Flavoring with substituted norbornane derivatives

ABSTRACT

Processes and compositions are described for the use in foodstuff, chewing gum, toothpaste and medicinal product flavor and aroma augmenting, modifying, enhancing and imparting compositions and as foodstuff, chewing gum, toothpaste and medicinal product aroma imparting materials of one or more substituted norbornane derivatives or mixtures of the same as follows: 
     
         ______________________________________                                    
 
    
     STRUCTURE OF COMPOUND                                                     
                    NAME OF COMPOUND                                      
______________________________________                                    
Mixture of &#34;cis&#34; and &#34;trans&#34;                                              
isomers of                                                                
 ##STR1##           2(2-butenoyl)-3,3-dimethyl- norbornane                
 ##STR2##           2-(3&#39;-butenoyl)-3,3-di- methyl-norbornane             
Mixture of &#34;cis&#34; and &#34;trans&#34;                                              
isomers of                                                                
 ##STR3##           endo-2(2&#39;-butenoyl)-3,3- dimethyl-5-norbornene        
 ##STR4##           3,3-dimethyl-2-(4&#39;- pentenoyl)-norbornane             
Mixture of                                                                
 ##STR5##           Mixture of 3,3-dimethyl- 2(4&#39;-methyl-4&#39;-pentenoyl)-   
                    norbornane and 3,3- dimethyl-2-acetyl- 2(2&#39;-methyl-2&#39;-
                    pro- penyl)-norbornane                                
and                                                                       
 ##STR6##                                                                 
Mixture of                                                                
 ##STR7##           Mixture of 3,3-dimethyl-2- (4&#39;-methyl -2&#39;-pentenoyl)- 
                    orbornane; 3,3-dimethyl-2- (4&#39;-methyl-3&#39;-pentenoyl)-  
                    norbornane; and 3,3- dimethyl-2-(4&#39;-methyl- 3-methoxy-
                    pentenoyl)- norbornane                                
and                                                                       
 ##STR8##                                                                 
and                                                                       
 ##STR9##                                                                 
Mixture of                                                                
 ##STR10##          Mixture of 3,3-dimethyl-2- (4&#39;-methyl                 
                    -2&#39;-pentenoyl)-5- norbornene; 3,3-dimethyl-2-         
                    (4&#39;-methyl-3-pentenoyl)-5- norbornane; and 3,3-       
                    dimethyl-2-(4&#39;-methyl- 3-methoxy-pentenoyl)-5-        
                    norbornene                                            
and                                                                       
 ##STR11##                                                                
and                                                                       
 ##STR12##                                                                
______________________________________

this application is a divisional of application for U.S. Patent Ser. No. 765,847, filed Feb. 4, 1977, now U.S. Pat. No. 4,076,853, issued on Feb. 28, 1978.

BACKGROUND OF THE INVENTION

The present invention relates to substituted norbornane derivatives of the genus of compounds having the structure: ##STR13## wherein each of the dashed lines represents a carbon-carbon single bond or a carbon-carbon double bond with the proviso that at least one of the dashed lines is a carbon-carbon single bond; wherein n is 0 or 1 with the proviso that n is 1 when both dashed lines are carbon-carbon single bonds and n is 0 when one of the dashed lines is a carbon-carbon double bond; wherein R₁ and R₂ are each the same or different hydrogen or lower alkyl; wherein Y is: ##STR14## wherein R₃ and R₄ are each alkyl; wherein R₇, R₈ and R₁₀ are each the same or different hydrogen or lower alkyl; wherein R₉ and R₉ ' taken separately are the same or different lower alkyl, or taken together is lower alkylene; wherein the dotted line represents a carbon-carbon single bond or a carbon-carbon double bond; and wherein each of the wavy lines represents, in the alternative, exo or endo isomers, produced by the novel processes of our invention, and to novel compositions using one or more of such substituted norbornane derivatives to alter, modify or enhance the flavor and/or aroma of consumable materials or impart flavor and/or aroma to consumable materials.

There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply, and to provide more uniform properties in the finished product.

Fruity, piney/green, winey, fruity-estery, cedarwood, floral, woody, balsam tree resin-like, sweet, fruity berry, incense, minty, balsam, blueberry, piney, green gruity and/or pine needle/green aromas with piney, eugenol/clove, spicey, fruity, winey, sweet, banana-like, estery, balsam tree resin-like, woody, incense, warm tea-like, floral, cedarwood, rosey, berry, tea astringent, bitter, camphoraceous green/earthy, green, minty, earthy, red beet-like, balsam natural-like, balsam resin-like, rum-like and/or blueberry tastes are particularly desirable for many uses in foodstuff flavors, chewing gum flavors, toothpaste flavors and medicinal product flavors.

Sweet, woody, fruity, cooling aroma prior to smoking and sweet, natural tobacco like smoke flavor characteristics in the mainstream on smoking are desirable in tobaccos and in tobacco flavoring compositions.

Intense and pleasant, twiggy, melony, sweet, woody, fruity, spicey (nutmeg, pepper), herbaceous, fir-balsam, thujone-like, cedar leaf, camphoraceous, musty, minty, fresh cut pine/spruce, artemesia, natural-like, cresylic, borneol aromas with strong armoise-like undertones are desirable in several types of perfume compositions, perfumed articles and colognes.

U.S. Pat. No. 3,852,358 issued on Dec. 3, 1974, discloses a process for producing 2-acetyl-3,3-dimethyl-5-norbornene in both the exo and endo forms which have uses in perfumery and other fragrance applications. These compounds have the structures: ##STR15## These compounds, produced by reaction of cyclopentadiene with mesityl oxide, are starting materials for producing a number of the compounds of our invention. However, the compounds of our invention have unexpected, unobvious and advantageous properties when compared with the 2-acetyl-3,3-dimethyl-5-norbornene of U.S. Pat. No. 3,852,358.

U.S. Pat. No. 3,942,761 discloses the use in perfumery of 4-(2'-norbornyl)-2-butanones having the structure: ##STR16## wherein R₁ is hydrogen or methyl and R is hydrogen or lower alkyl containing from 1 to 8 carbon atoms. Such compounds have structures which are different in kind from the structures of the compounds of our invention. Also disclosed as intermediates for producing the foregoing compounds are compounds having the generic structure: ##STR17## wherein the dotted line is a carbon-carbon single bond or a carbon-carbon double bond. In addition, the following reaction sequence is set forth therein: ##STR18##

Arctander, "Perfume and Flavor Chemicals", 1969, Vol. 1, discloses the use in perfume compositions and in foodstuff flavors of "fenchone", "fenchyl alcohol", "camphene carbinol", and "camphene carbinyl acetate", thus:

(i) "1385: FENCHONE

laevo-Fenchone. (dextro- is known but less common as a fragrance material).

1,3,3-Trimethyl-2-norbornanone.

1,3,3-Trimethyl bicyclo-1,2,2-heptanone-2. ##STR19## Warm-camphoraceous, powerful and diffusive, basically sweet odor. Warm, somewhat burning and bitter taste with a medicinal note.

This ketone finds some use as a masking odor in industrial fragrances. It is also used in the reconstruction of Fennel oil and a few other essential oils.

In spite of its rather unpleasant taste, it is used in various Berry complex flavors, in Spice complexes and in certain types of Liquer flavoring.

The concentration used is about 0.1 to 5 ppm in the finished product".

(ii) "1387: FENCHYL ALCOHOL

1,3,3-trimethyl-2-norbornanol.

1,3,3-Trimethyl bicyclo-1,2,2-heptanol-2.

2-Fenchanol.

Fenchol. ##STR20## The racemic alpha-Fenchol has a somewhat lower melting point, and the beta-Fenchols are all liquid at room temperature.

Fenchol made by reduction of Fenchone from Cedarleaf oil is usually a mixture of several isomers, including the crystalline alpha-isomers. The beta-isomer forms a crystalline Hydrate which may be solid at room temperature.

Almost insoluble in water, soluble in alcohol, miscible with oils. Powerful and diffusive, Camphor-like, but sweeter and more Citrus-like almost Lime-like odor with more or less of an earthy-dry character, according to the composition and isomer-ratio.

The taste is somewhat bitter-Lime-like, camphoraceous and slightly woody-musty.

This interesting alcohol (or mixed alcohols) finds use in perfume compositions ranging from woody or herbaceous to Citrus-Lime and even certain floral types. It produces power and "lift" to floral fragrances, and solid background to Lime and other Citrus bases, having the advantage over the Terpenes in being very stable in soap.

Fenchyl alcohol is also used in flavor compositions such as Strawberry and other berries, Lime and Spice, etc.

The concentration is normally low, e.g. 0.2 up to 5 ppm in the finished product".

(iii) "1028: 3,3-DIMETHYL-Δ², beta-NORBORNANE-2-ETHANOL "Camphene carbinol". ##STR21## Sweet-camphoraceous, warm and soft odor with a woody undertone. Upon standing it may develop an odor resembling that of Celluloid.

Although rarely offered commercially, this chemical could find some use in perfume compositions of the woody, Oriental and orrisy type, in new variations of Pine fragrances, and in various soap and detergent perfumes".

(iv) "1029: 3,3-DIMETHYL-Δ² -beta-NORBORNANE-2-ETHYLACETATE

"camphene carbinyl acetate". ##STR22## Mild and sweet-woody odor with a floral-piney undertone. The commercial products are probably not well-defined single chemicals, and great variations in odor have been observed.

This ester has been developed in line with the research on Sandalwood type odors. The parent alcohol "Camphene carbinol" was once considered useful as a Sandalwood type material, but it has found more use as a sweetening and enriching ingredient in sophisticated Pine fragrances. The title ester finds limited use in perfume compositions of woody character, Fougeres, Pine fragrances, etc. and it blends very well with the Cyclohexanol derivatives, Ionones, iso-Bornylacetate, Nitromusks, etc.".

U.S. Pat. No. 3,928,456 discloses monocyclic compounds having the generic structure: ##STR23## containing one double bond in position 2'- or 3'- of the acyl side-chain and either one double bond in position 1- or 2-(as shown in the above formula, the double bond in the 2 position can be either in the cycle or the side chain), or two conjugated double bonds in positions 1- and 3- of the cycle, the double bonds being represented by dotted lines, and wherein n is zero or 1, R¹, R² and R³ represent hydrogen or one of them a lower alkyl radical, such as methyl or ethyl, and the others hydrogen, and R⁴, R⁵, R⁶ and R⁷ represent hydrogen or one of them a lower alkyl radical, such as methyl or ethyl, and the others hydrogen, as being useful in perfumery and food flavors and also flavors, beverages, animal feeds and tobaccos. Specifically disclosed in this patent is a compound having the structure: ##STR24##

U.S. application for Patent Ser. No. 551,030, filed on Feb. 19, 1975 discloses, interalia, perfumery uses of compounds having the structures: ##STR25## wherein one of the dashed lines is a carbon-carbon bond and each of the wavy lines is a carbon-carbon single bond, one of the carbon-carbon single bonds represented by the wavy line being epimeric with respect to the other of the carbon-carbon single bonds represented by the wavy line.

In addition, various processes and compounds relating to the synthesis of synthetic sandalwood oil components are described in the following U.S. Pat. Nos.

(i) Perfume Compounds And Process For Preparing Same--3,673,261 issued June 27, 1972:

Compounds: ##STR26## 2-methylene-3-exo-(trans-4'-methyl-5'-hydroxypent-3'-enyl)-bicyclo[2.2.1]heptane; trans-3-normethyl-beta-santalol ##STR27## 2-methylene-3-exo-(cis-4'-methyl-5'-hydroxypent-3'-enyl)-bicyclo[2.2.1]heptane; cis-3-normethyl-beta-santalol ##STR28## 2-methylene-3-exo-(4'-methyl-5'-hydroxypentyl)-bicyclo[2.2.1]heptane; 3-normethyldihydro-beta-santalol

(ii) Dihydro-beta-santalol and Processes For Preparing Dihydro-beta-santalol From 3-Endo-Methyl-3-Exo-(4'-Methyl-5'-Hydroxyphenyl)-Norcamphor--3,673,263 issued June 27, 1972: ##STR29##

dihydro-beta-santalol

(iii) Process For Preparing Beta-Santalol From 3-Methylnorcamphor--3,662,008 issued May 9, 1972: ##STR30##

endo-3-methyl-exo-3-(cis-5'-hydroxy-4'-methylpent-3'-enyl)-2-methylenebicyclo[2.2.1]heptane ##STR31## endo-3-methyl-exo-3-(trans-5'-hydroxy-4'-methylpent-3'-enyl)-2-methylenebicyclo[2.2.1]heptane

(iv) Process For Preparing Dihydro-Beta-Santalol From 3-Endo-Methyl-3-Exo-(4'-Methyl-5'-Hydroxypentyl)-Norcamphor--3,673,266, issued June 27, 1972: ##STR32##

dihydro-beta-santalol

None of the compounds disclosed in either U.S. Pat. No. 3,928,456 or U.S. application for Patent Ser. No. 551,030, filed Feb. 19, 1975 have properties even closely similar to the properties of the compounds of the instant application.

Chem. Abstracts, Vol. 84, 73728n (abstract of Karaev, et al, Zh.Org.Khim. 1975, 11(12), 2622) discloses preparation of the compound: ##STR33## followed by isomerization with HgO/H₂ SO₄.

Klein and Rojahn, Chem. Abstracts, Vol. 84, 90327y (1976) discloses the use of compounds having the structure: ##STR34## (wherein the dashed line is a single or double bond) as an intermediate in the preparation of beta-santalol; but no organoleptic properties of these norbornane derivatives are disclosed.

U.S. Pat. No. 3,748,344, issued on July 24, 1973, discloses that chemical compounds characterized by the structural formula: ##STR35## wherein the dashed line represents the presence of a single or a double bond wherein R₁ ', R₂ ', R₃ ', and R₄ ' each represent hydrogen or lower methyl and R₅ ' represents hydrogen or lower alkyl and R₆ ' represents a polymethylene radical of from 2 to 4 carbon atoms which is unsubstituted or substituted with lower alkyl, which "as a whole exhibits a characteristic, pleasant, strong and long lasting aroma which is highly useful in the preparation of fragrance compositions and perfume products". Various notes are described such as green, cuminic, walnut, raw potato, earthy, camphoraceous, civet, walnut bark, neroli, anise, vegetable, menthone, animal, minty, eucalyptol, cucumber, pine and fecal. The specific ketals of our invention are not disclosed in U.S. Pat. No. 3,748,344.

In addition, U.S. Pat. No. 3,748,344 discloses as chemical intermediates for preparing the above ketal, a compound having the generic structure: ##STR36## wherein R₁ ', R₂ ', R₃ ', R₄ ', and R₅ ' have the same meaning as defined above.

However, the specific genuses and compounds of our invention are not set forth in U.S. Pat. No. 3,748,344 and all uses of them as chemical intermediates for this genus of ketones is set forth in 3,748,344 at column 3, lines 61-70.

No prediction of the organoleptic properties of the compounds of the instant invention can be made by a study of the disclosure of 3,748,344.

Chemical Abstracts, Vol. 71, 49664z (abstract of Sadykh-Zade, et al (U.S.S.R.). Dokl. Akad. Nauk Azerb. SSR 1968, 24(11), 38-41) discloses the synthesis of exo and endo forms of the compounds having the structures: ##STR37##

Chemical Abstracts, Vol. 81, 135512m (abstract of Akhmedov, I. M., et al (Inst. Georg. Fiz. Khim., Baku, U.S.S.R.). Dokl. Akad. Nauk Az. SSR 1974, 30(4), 18-21) discloses the synthesis of the compound having the structure: ##STR38##

None of the Chemical Abstracts references discloses compounds which have a close structural relationship to the compound of the instant invention. In any event, the organoleptic properties of the compounds of the Chemical Abstract references are different in kind from those of the compounds of the instant invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the NMR spectrum of the compound having the structure: ##STR39## as synthesized in Example II.

FIG. 2 illustrates the Infrared spectrum of the compound having the structure: ##STR40## as synthesized in Example II.

FIG. 3 illustrates the NMR spectrum of the cis isomer, having the structure: ##STR41## produced according to Example III.

FIG. 4 illustrates the Infrared spectrum of the cis isomer, having the structure: ##STR42## as synthesized in Example III.

FIG. 5 illustrates the NMR spectrum of the compound having the structure: ##STR43## as synthesized in Example III.

FIG. 6 illustrates the Infrared spectrum of the compound having the structure: ##STR44## as synthesized in Example III.

FIG. 7 illustrates the NMR spectrum of the compound having the structure: ##STR45## as synthesized in Example XI.

FIG. 8 illustrates the Infrared spectrum of the compound having the structure: ##STR46## as synthesized in Example XI.

FIG. 9 illustrates the NMR spectrum for fraction 7 of Example XII containing primarily a compound having the structure: ##STR47##

FIG. 10 illustrates the Infrared spectrum for fraction 7 of Example XII containing primarily a compound having the structure: ##STR48##

FIG. 11 illustrates the NMR spectrum for fraction 5 of Example XVI which is a compound having the structure: ##STR49##

FIG. 12 illustrates the Infrared spectrum for fraction 5 of Example XVI which is the compound having the structure: ##STR50##

FIG. 13 illustrates the NMR spectrum for fraction 5 of Example XVII which is the compound having the structure: ##STR51##

FIG. 14 illustrates the Infrared spectrum for fraction 5 of Example XIX which is a compound having the structure: ##STR52##

FIG. 15 illustrates the GLC profile of the mixture produced according to Example XIX.

FIG. 16 is an illustration of the NMR spectrum of the mixture of three compounds in fraction 12 of Example XIX, the three compounds having the structures: ##STR53##

FIG. 17 illustrates the Infrared spectrum of fraction 12 of Example XIX which is a mixture of the three compounds having the structures: ##STR54##

FIG. 18 illustrates the NMR spectrum of peak 1 from fraction 18 of Example XIX, which is a mixture of the two ketones having the structures: ##STR55##

FIG. 19 illustrates the Infrared spectrum of peak 1, fraction 18 of Example XX, which is a mixture of the two ketones having the structures: ##STR56##

FIG. 20 illustrates the NMR analysis of the keto ether produced according to Example XX, having the structure: ##STR57##

FIG. 21 illustrates the Infrared spectrum for the keto ether having the structure: ##STR58## produced according to Example XX.

FIG. 22 illustrates the GLC profile for the mixture of ketones and keto ethers produced according to Example XX, having the structures: ##STR59##

FIG. 23 is an illustration of the NMR spectrum for the mixture of ketones and keto ethers produced according to Example XX, having the structures: ##STR60##

FIG. 24 is the Infrared spectrum for the mixture of ketones and keto ethers produced according to Example XX.

FIG. 25 illustrates the NMR spectrum of the compound having the structure: ##STR61## produced according to Part A of Example XXI (fraction 4).

FIG. 26 illustrates the Infrared spectrum of the compound having the structure: ##STR62## produced according to Part A of Example XXI (fraction 4).

FIG. 27 illustrates the NMR spectrum for the compound having the structure: ##STR63## produced according to Part B of Example XXI (fraction 2).

FIG. 28 illustrates the Infrared spectrum for the compound having the structure: ##STR64## produced according to Part B of Example XXI (fraction 2).

FIG. 29 illustrates the NMR spectrum for fraction 4 of Example XXII, which is a compound having the structure: ##STR65##

FIG. 30 is the Infrared spectrum for fraction 4 of Example XXII, which is a compound having the structure: ##STR66##

FIG. 31 is the GLC profile for the mixture produced according to the reaction of Example XXIII, which mixture contains compounds having the structures: ##STR67##

FIG. 32 illustrates the NMR spectrum for the compound having the structure: ##STR68## produced according to Example XXIV.

FIG. 33 illustrates the NMR spectrum for the compound having the structure: ##STR69## produced according to Example XXIV.

FIG. 34 illustrates the NMR spectrum for the compound having the structure: ##STR70## produced according to Example XXIV.

FIG. 35 is the Infrared spectrum for the compound having the structure: ##STR71## produced according to Example XXIV.

FIG. 36 illustrates the NMR spectrum for the compound produced in Part A of Example XXIV, having the structure: ##STR72##

FIG. 37 illustrates the Infrared spectrum for the compound produced in Part A of Example XXIV having the structure: ##STR73##

FIG. 38 is the NMR spectrum for the compound produced in Part B of Example XXIV having the structure: ##STR74##

FIG. 39 is the Infrared spectrum for the compound produced in Part B of Example XXIV having the structure: ##STR75##

FIG. 40 is the NMR spectrum for the compound having the structure: ##STR76## produced according to Example XXVI.

FIG. 41 is the Infrared spectrum for the compound having the structure: ##STR77## produced according to Example XXV.

FIG. 42 illustrates the NMR spectrum for the compound having the structure: ##STR78## produced according to the process of Example XXVI.

FIG. 43 illustrates the Infrared spectrum for the compound having the structure: ##STR79## produced according to the process of Example XXVI.

FIG. 44 illustrates the NMR spectrum for the compound having the structure: ##STR80## produced according to the process of Example XXVII.

FIG. 45 illustrates the Infrared spectrum for the compound having the structure: ##STR81## produced according to the process of Example XXVII.

FIG. 46 illustrates the NMR spectrum for the compound having the structure: ##STR82## produced according to the process of Example XXVII.

FIG. 47 is the Infrared spectrum for the compound having the structure: ##STR83## produced according to the process of Example XXVII.

FIG. 48 is the NMR spectrum for the compound having the structure: ##STR84## produced according to the process of Example XXVII.

FIG. 49 is the Infrared spectrum for the compound having the structure: ##STR85## produced according to the process of Example XXVII.

FIG. 50 is the GLC profile for the mixture (i) of the reaction product of Example XXX, b.p. 100°-111° C./0.9 mm Hg.

FIG. 51 is the NMR spectrum for the compound having the structure: ##STR86## produced according to the process of Example XXX.

FIG. 52 is the Infrared spectrum for the compound having the structure: ##STR87## produced according to the process of Example XXX.

FIG. 53 is the NMR spectrum for the compound having the structure: ##STR88## produced according to the process of Example XXX.

FIG. 54 is the Infrared spectrum for the compound having the structure: ##STR89## produced according to the process of Example XXX.

FIG. 55 is the NMR spectrum for the compound having the structure: ##STR90## produced according to the process of Example XXX.

FIG. 56 is the Infrared spectrum for the compound having the structure: ##STR91## produced according to the process of Example XXX.

FIG. 57, FIG. 58, FIG. 59 and FIG. 60 represent GC-MS profiles for compounds produced according to the process of Example XXXI.

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff, chewing gum, medicinal product and toothpaste compositions and flavoring compositions therefor having fruity, piney/green, winey, fruity-estery, cedarwood, floral, woody, balsam tree resin-like, sweet, fruity berry, incense, minty, balsam, blueberry, piney, green fruity and/or pine needle/green aromas with piney, eugenol/clove, spicey, fruity, winey, sweet, banana-like, estery, balsam tree resin-like, woody, incense, warm tea-like, floral, cedarwood, rosey, berry, tea, astringent, bitter, camphoraceous green/earthy, green, minty, earthy, red beet-like, balsam natural-like, balsam resin-like, rum-like and/or blueberry tastes; as well as novel tobacco and tobacco flavoring compositions having sweet, woody, fruity, cooling aroma prior to smoking and sweet, natural tobacco-like smoke flavor characteristics in the mainstream on smoking; as well as novel perfume compositions, colognes and perfumed articles having intense and pleasant, twiggy, melony, sweet, woody, fruity, spicey (nutmeg, pepper), herbaceous, fir-balsam, thujone-like, cedar leaf, camphoraceous, musty, minty, fresh cut pine/spruce, artemesia, natural-like, cresylic, borneol aromas with strong armoise-like undertones, may be provided by the utilization of one or more substituted norbornane derivatives having the generic structure: ##STR92## wherein each of the dashed lines represents a carbon-carbon single bond or a carbon-carbon double bond with the proviso that at least one of the dashed lines is a carbon-carbon single bond; wherein n is 0 or 1 with the proviso that n is 1 when both dashed lines are single bonds and n is 0 when one of the dashed lines is a double bond; wherein R₁ and R₂ are each the same or different hydrogen or lower alkyl; wherein Y is: ##STR93## wherein R₃ and R₄ are each alkyl; wherein R₇, R₈ and R₁₀ are each the same or different hydrogen or lower alkyl; wherein R₉ and R₉ ' taken separately are the same or different lower alkyl, or taken together is lower alkylene; wherein the dotted line represents a carbon-carbon single bond or a carbon-carbon double bond; and wherein each of the wavy lines represents, in the alternative, exo or endo isomers, in foodstuffs, chewing gums, toothpastes, medicinal products, perfume compositions, perfumed articles, colognes and tobaccos as well as tobacco substitutes.

Unless otherwise specified, representations herein of carbon-carbon double bonds are intended to indicate a "cis" isomer, a "trans" isomer, or a mixture of "cis" and "trans" isomers with respect to that carbon-carbon double bond.

The novel substituted norbornane derivatives of our invention useful as indicated supra, may be produced, preferably, by one of several processes:

(1) A process comprising the step of reacting one or a mixture of compounds having the structures: ##STR94## wherein the dotted line represents a carbon-carbon single bond or a carbon-carbon double bond with an aldehyde having the structure: ##STR95## wherein R₁ and R₁₀ are the same or different alkyl or hydrogen as defined above, thereby forming a mixture of compounds having the two structures: ##STR96## utilizing the resulting compounds for their organoleptic properties or further reacting the resulting compounds, either with a Grignard reagent, R₈ MgX, or an organolithium reagent, R₈ Li, (wherein R₈ is lower alkyl, e.g., methyl, ethyl, 1-propyl-2-propyl, 1-butyl, 2-butyl, 2-methyl-1-butyl or 2-methyl-2-butyl) followed by hydrolysis to form the tertiary alcohol having one of the structures: ##STR97## or by reduction of the carbonyl group and/or one (or more) of the carbon-carbon double bond(s) to form the secondary alcohol or ketone having one of the structures: ##STR98## or by re-arranging the carbon-carbon double bond in the side chain thereby forming compounds of the structure: ##STR99## wherein R₁ and R₁₀ are the same or different hydrogen or lower alkyl, wherein the dotted line represents a carbon-carbon single bond or a carbon-carbon double bond, and wherein each of the dashed lines represent a carbon-carbon single bond or a carbon-carbon double bond with the proviso that at least one of the dashed lines is a carbon-carbon single bond.

(2) Oxidizing camphene to form camphene oxide having the structure: ##STR100## and then rearranging said camphene oxide to the aldehyde (3,3-dimethylnorbornane-2-carboxaldehyde) having the structure: ##STR101## and then reacting the aldehyde with a Grignard reagent having the structure: ##STR102## or an organolithium reagent having the structure: ##STR103## wherein X is one of the halogen atoms, chlorine, bromine or iodine, thereby forming an organometallic compound having the structure: ##STR104## and then hydrolyzing the said organometallic compound to form the corresponding alcohol having the structure: ##STR105## and then using said alcohol for its organoleptic properties or oxidizing or reducing said alcohol to form either the unsaturated ketone, or the saturated alcohol, as is set forth in the first of these processes (process (1)), which ketone and alcohols have the structures, respectively, ##STR106## and then using the resulting products for their organoleptic properties or, in the case of compounds having unsaturation in the side chain, rearranging the double bond to form a compound having the structure: ##STR107## (3) Reacting an aldehyde having the structure: ##STR108## with a Grignard reagent having the structure: ##STR109## or an organolithium reagent having the structure: ##STR110## wherein n is 0 or 1 thereby forming an organometallic compound having the structure: ##STR111## then hydrolyzing the resulting organometallic compound thereby forming the saturated alcohol having the structure: ##STR112## This alcohol can then be used as such for its organoleptic properties or it can be oxidized to form the ketone having the structure: ##STR113## or it can be esterified with an esterification agent to form an ester having the structure: ##STR114## wherein R₁, R₂ and R₃ are the same or different hydrogen or alkyl and n is 0 or 1.

(4) Adding a compound, 2-acetyl-3,3-dimethyl-5-norbornene having the structure: ##STR115## to acetaldehyde according to the reaction sequence: ##STR116## (wherein X is halogen, e.g., chloro, bromo or iodo) whereby a compound having the structure: ##STR117## is formed. (5) Adding 2-acetyl-3,3-dimethylnorbornane having the structure: ##STR118## to an allylic halide having the structure: ##STR119## wherein either or both of R₁, R₂ and R₁₀ is hydrogen or lower alkyl and X is one of the halogen atoms, chlorine, bromine or iodine, in the presence of a base such as an alkali metal hydroxide and a "phase transfer agent", or in the presence of a base such as an alkali metal hydride in the presence of a "phase transfer agent" in order to form the compounds having the structures: ##STR120## wherein any of R₁, R₂, R₁₀, R₁ ', R₂ ' and R₁₀ ' are the same or different hydrogen or lower alkyl; using the resulting mixture "as is" for its organoleptic properties or separating the resulting mixture into its component compounds and using the resulting compounds for their organoleptic properties or further reacting the resulting mixture or each of the resulting compounds as by rearrangement of a carbon-carbon double bond and/or by reduction of the keto group to form a hydroxyl group or reduction of one or more carbon-carbon double bonds using hydrogen;

(6) Reacting 2-acetyl-3,3-dimethylnorbornane or 2-acetyl-3,3-dimethyl-5-norbornene with a dialkyl carbonate to form a ketocarboxylic acid ester, forming the enolate of the ketocarboxylic acid ester using a base, and then reacting the resulting enolate with an allyl halide to form a substituted ketocarboxylic acid ester and saponifying the resulting substituted ketocarboxylic acid ester to form a salt of a ketocarboxylic acid and then acidifying the salt of the ketocarboxylic acid and decarboxylating the ketocarboxylic acid according to the following reaction sequence: ##STR121## wherein R₆ is lower alkyl and R₁ and R₂ are the same or different hydrogen or lower alkyl, M₁ and M₂ are the same or different alkali metal; using the resulting ketone "as is" for its organoleptic properties or further reacting the resulting ketone as indicated in any of Processes 1-5, inclusive;

(7) Reacting 2-acetyl-3,3-dimethylnorbornane or 2-acyl-3,3-dimethyl-5-norbornene having the generic structure: ##STR122## wherein R₈ ' is lower alkyl, with an allylic Grignard reagent having the structure: ##STR123## or an allylic lithium reagent having the structure: ##STR124## wherein X is one of the halogen atoms, chlorine, bromine or iodine, thereby forming an organometallic compound having the structure: ##STR125## and then hydrolyzing the organometallic compound using aqueous mineral acid to form the corresponding tertiary alcohol having the generic structure: ##STR126##

Each of the foregoing processes is described below in more detail.

Process 1:

The reaction of the aldehyde having the structure: ##STR127## with 2-acetyl-3,3-dimethylnorbornane or 2-acetyl-3,3-dimethyl-5-norbornene, preferably takes place in the presence of either a base such as an alkali metal hydroxide (e.g., NaOH) or a mixed catalyst containing boron oxide and boric acid whereby an alkenoyl norbornane or norbornene derivative is formed having the structure: ##STR128## wherein one of the dashed lines is a carbon-carbon double bond and the other is a single bond and the dotted line represents a carbon-carbon single bond or double bond; wherein R₁ and R₁₀ are the same or different hydrogen or lower alkyl. Thus, for example, reaction of acetaldehyde with 2-acetyl-3,3-dimethylnorbornane produces 2-(trans-2-butenoyl)-3,3-dimethylnorbornane. It is preferred to carry out this reaction at a temperature in the range of from 120° C. up to 200° C. for a period of from 3 up to 10 hours. It is preferred that the mole ratio of 2-acetyl-3,3-dimethylnorbornane (or norbornene) aldehyde be 1:1 or slightly greater than 1:1. When using an alkali metal hydroxide catalyst, it is preferred that the mole ratio of base:acetyl norbornane or norbornene be from 1:1 up to 20:1. When using the mixed catalyst, boron oxide:boric acid, it is preferred that the mole ratio of aldehyde:boron oxide be approximately 2:1 or greater than 2:1 and it is preferred that the mole ratio of boron oxide:boric acid be between 5:1 and 10:1 with a preferred ratio range of between 6:1 and 8:1. In view of the temperature range of reaction, 120°-180° C., this reaction is carried out in an autoclave at autogeneous pressure. The resulting product can be used "as is" for its organoleptic properties or it can further be reacted with an R₈ MgX (e.g. CH₃ MgBr) Grignard reagent or R₈ Li wherein R₈ is lower alkyl in a solvent (e.g., tetrahydrofuran or diethyl ether) followed by acid hydrolysis (e.g., dilute HCl) or it can further be reduced using hydrogen as a reducing agent and a hydrogenation catalyst such as 5% palladium-on-carbon or Raney nickel. In place of the boric acid:boron oxide catalyst this reaction can be carried out using only boron oxide, and in that case, it is preferred to use a temperature of between 170°-185° C. at a pressure in the autoclave of between 40-100 psig.

Process 2:

The camphene epoxide is prepared from reaction of camphene with a peralkanoic acid oxidizing agent, for example, peracetic acid or perpropionic acid. It is also preferred that the reaction take place from 0° up to 80° C. (preferably, 40°-60° C.) in the presence of a solvent inert to the reactants or the reaction product. Such an inert solvent is methylene chloride. Other useful inert solvents are benzene, toluene, xylene and cyclohexane. The mole ratio of camphene:peracetic acid is preferably slightly less than 1:1 since it is desired that all the camphene be reacted. At the end of the reaction any excess peracetic acid is neutralized and the camphene oxide may be isolated or the reaction mass may be used "as is" for the subsequent reaction. From an economic standpoint, it is preferred that the reaction mass be used "as is" rather than purify the camphene oxide.

The resulting product is then rearranged to the aldehyde by heating with MgCl₂ or MgBr₂, and the resulting aldehyde is then admixed with a prepared Grignard reagent having the formula: ##STR129## or organolithium reagent having the structure: ##STR130## wherein X is one of the halogen atoms chlorine, iodine or bromine and R₁ and R₂ are the same or different hydrogen or lower alkyl. It is preferred that the Grignard reagent and the aldehyde each be respectively dissolved in appropriate solvents prior to admixing the aldehyde with the Grignard reagent. Suitable solvents for the reaction are tetrahydrofuran, diethyl ether, and mixtures of tetrahydrofuran or diethyl ether with benzene, toluene, xylene, or cyclohexane. It is preferred that reaction of the Grignard reagent or organolithium compound with the aldehyde take place at a temperature in the range of from 50° C. up to 100° C. at atmospheric pressure, preferably in the range of 65°-70° C. The resulting organometallic compound is then hydrolyzed with aqueous acid, preferably an aqueous protonic acid such as hydrochloric acid or phosphoric acid, whereby the pH of the resulting solution is approximately 1. The resulting alcohol, the hydrolyzed product, is then extracted from the reaction mass with a suitable inert extraction solvent such as benzene, toluene or xylene and is then isolated by means of evaporation and fractional distillation. The resulting alcohol may then be used "as is" for its organoleptic properties in perfumery, as a flavorant for foodstuffs, in chewing gums, medicinal products or tobaccos or as a flavor for tobacco; or it may further be reacted as by oxidation or reduction.

The oxidation of the alcohol is carried out using a suitable oxidation agent such as "Jones Reagent", sodium dichromate-sulfuric acid mixture, pyridinium chlorochromate, or a chromium trioxide-acetic acid-water mixture to form the corresponding ketone. The oxidation reaction may be carried out at temperatures between -10° C. and +50° C. When using a Jones Reagent, it is preferred to use a temperature of about -5° C. It is noteworthy that oxidation systems such as dimethyl sulfoxide-acetic anhydride or copper chromite have not given successful oxidations. The resulting ketone may be hydrogenated using, for example, a palladium catalyst or a palladium-on-carbon catalyst, whereby a saturated ketone is formed for example, according to the reaction: ##STR131## or the ketone can be used "as is" for its organoleptic properties. The hydrogenation is preferably carried out at temperatures in the range of from about 20° C. up to 100° C.

Process 3:

In the reaction of 3,3-dimethylnorbornane-2-carboxaldehyde with the Grignard reagent having the structure: ##STR132## or the hydrocarbyl lithium compound having the structure: ##STR133## wherein n is 0 or 1, either or both of R₁ or R₂ is hydrogen or lower alkyl and X is one of the halogen atoms, chlorine, bromine or iodine, the reaction conditions are essentially the same as those of the corresponding reaction in Process 2 and the recovery steps are essentially the same. The resulting alcohol having the structure: ##STR134## can be used as such for its organoleptic properties or it can be oxidized to form a ketone under the conditions set forth in Process 2 or it can be esterified with an esterification agent to form an ester having the structure: ##STR135## wherein R₃ is hydrogen or lower alkyl. Esterification agents are alkanoic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride; mixed anhydrides such as acetic-propionic anhydride; acyl halides such as acetyl chloride, propionyl chloride, acetyl bromide propionyl bromide, n-butanoyl chloride, i-butanoyl chloride, n-pentanoyl chloride, n-octanoyl chloride, and n-lauroyl chloride.

Process 4:

The reaction sequence: ##STR136## involves a reaction of methyl aniline with methyl magnesium halide (chloride, bromide or iodide) preferably each in an appropriate solvent such as benzene/tetrahydrofuran, tetrahydrofuran or diethyl ether. It is also preferred that the mole ratio of methyl aniline:methyl magnesium halide be 1:1. It is further preferred that the reaction temperature producing the compound having the structure: ##STR137## is from -5° C. up to about 40° C. with the most preferred temperature being 20°-30° C. The reaction of the above compound with acetaldehyde preferably takes place in the presence of an appropriate solvent such as benzenetetrahydrofuran, tetrahydrofuran, or diethyl ether at a temperature in the range of from -5° C. up to 20° C., with a preferred temperature of 0° C. The hydrolysis to form the keto alcohol is carried out using a mineral acid such as dilute aqueous hydrochloric acid, sulfuric acid or phosphoric acid or other protonic acids such as paratoluenesulfonic acid. The hydrolysis preferably takes place at 0° C. The dehydration reaction using the keto alcohol is carried out with a mild dehydrating agent such as a mixture of acetic anhydride and sodium acetate at a temperature in the range of 80°-150° C. over a period of time of from about 1 up to 5 hours. The dehydration can also be carried out using a strong acid in a refluxing inert solvent, e.g., using a benzene-paratoluenesulfonic acid mixture. At the end of this reaction the excess dehydration agent, e.g. acetic anhydride, is destroyed and the reaction product isolated. Using this reaction sequence, only "trans" isomer is formed. If the starting material is "endo" 2-acetyl-3,3-dimethyl-5-norbornene, then the final product will also be an "endo" isomer. By the same token, if the starting material is "exo" 2-acetyl-3,3-dimethyl-5-norbornene, then the final product will be an "exo" isomer. Standard isolation techniques are used, e.g. fractional distillation and, if desired, preparative GLC for isolation of the end product.

Process 5:

The reaction of 2-acetyl-3,3-dimethylnorbornane with the allyl chloride derivative takes place after first forming the enolate of the 2-acetyl-3,3-dimethylnorbornane, thusly: ##STR138## The reagent used to form such enolate is preferably a hydride such as sodium hydride and potassium hydride. The enolate is then reacted with the allyl halide having the structure: ##STR139## wherein R₁ and R₂ are the same or different hydrogen or lower alkyl and X is one of the halogen atoms, chlorine, bromine or iodine. In addition, a similar result may be obtained when using an alkali metal hydroxide in the presence of a phase transfer agent whereby the reactants for the process and the base, respectively, are in two immiscible phases and the phase transfer agent may be one or more of several quaternary salts. Specific examples of phase transfer agents useful in our invention are as follows:

Tricapryl methyl ammonium chloride;

Cetyl trimethyl ammonium bromide; and

Benzyl trimethyl ammonium hydroxide.

In general, the phase transfer agents most preferred have the generic formula: ##STR140## wherein at least one of R₁₁, R₁₂, R₁₃ and R₁₄ is C₆ -C₁₄ aryl, C₆ -C₁₀ aralkyl, C₆ -C₂₀ alkyl, C₆ -C₁₄ alkaryl and C₆ -C₂₀ alkenyl and the other of R₁₂, R₁₃, R₁₄ is alkyl such as methyl, ethyl, n-propyl, i-propyl, 1-butyl, 2-butyl, 1-methyl-2-propyl, 1-pentyl and 1-octyl and Z⁻ is an anion such as chloride, bromide and hydroxide. Furthermore, this process is carried out in an inexpensive solvent which is inert to the reaction system such as toluene, benzene, o-xylene, m-xylene, p-xylene, ethyl benzene, n-hexane, cyclohexane, methylene chloride and o-dichlorobenzene. This Process (5) of our invention is carried out at a temperature in the range of from about 10° C. up to about 150° C. with a temperature range of 50°-120° C. being preferred. The reaction time is inversely proportional to the reaction temperature, with lower reaction temperatures giving rise to greater reaction times; and, accordingly, the reaction time ranges from about 30 minutes up to about 10 hours.

In this reaction of our invention the mole ratio of 2-acetyl-3,3-dimethylnorbornane:allyl halide reactant is in the range of from 0.5:1.5 up to 1.5:0.5 with a preferred ratio of norbornane:allyl halide being from 1:1 up to 1:1.2.

The quantity of "phase transfer agent" in the reaction mass, based upon the amount of 2-acetyl-3,3-dimethylnorbornane in the reaction mass, may vary from 0.5 grams of "phase transfer agent" per mole of norbornane derivative to 25 grams of "phase transfer agent" per mole of norbornane derivative with a preferred concentration of "phase transfer agent" being in the range of from 2.5 up to 7.5 grams of "phase transfer agent" per mole of norbornane derivative.

Process (5) of our invention is preferably carried out at atmospheric pressure since that it the most convenient condition. However, lower or higher pressures can be used without detrimentally affecting the ultimate yield of desired reaction product.

Process 6:

The initial compound formed is that created by reaction of the dialkyl carbonate with 2-acetyl-3,3-dimethylnorbornane in the presence of an alkali metal hydride, as illustrated by the following reaction: ##STR141## wherein R₆ is alkyl having from 1 up to 8 carbon atoms, but most conveniently ethyl. The reaction is preferably carried out under reflux conditions using a solvent inert to the reactants such as benzene, toluene or xylene. The mole ratio of norbornane derivative: dialkyl carbonate is preferably 1:2; but can vary from 1:1 up to 1:5. The ratio of base:dialkyl carbonate is preferably 1:1.

The reaction of the resulting beta-ketocarboxylic acid ester with the allyl halide having the structure: ##STR142## (wherein X is a halogen, chlorine, bromine or iodine and R₁, R₂ and R₁₀ are the same or different hydrogen or lower alkyl), is carried out in the presence of approximately one equivalent of base such as an alkali metal hydride or alkali metal alkoxide or hydroxide in the presence of a suitable solvent. A "phase transfer agent" may be used.

The ketocarboxylic acid ester derivative has the structure: ##STR143## This ketocarboxylate, (a novel genus of compounds), is then saponified using standard techniques such as with an aqueous base such as 5-25% aqueous sodium hydroxide or potassium hydroxide, and the resulting alkali metal salt having the structure: ##STR144## (wherein M is alkali metal), is then neutralized and simultaneously decarboxylated using aqueous mineral acid such as sulfuric acid or aqueous hydrochloric acid. The resulting reaction product having the structure: ##STR145## (a mixture of cis and trans isomers; wherein R₁ and R₂ is alkyl) may then be used for its organoleptic properties "as is" or it may be hydrogenated with hydrogen using a catalyst such as palladium, palladium-on-carbon or Raney nickel, whereupon the carbon-carbon double bond in the side chain is reduced to a carbon-carbon single bond thereby forming a compound having the structure: ##STR146## Both the unsaturated ketone and the saturated ketone may be reacted, if desired, with an alcohol or glycol in the presence of sulfuric acid or hydrochloric acid thereby forming a ketal according to the reaction: ##STR147## wherein R₉ and R₉ ' each represent lower alkyl taken separately or, when taken together, represents lower alkylene, e.g. ethylene; and wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond. Alternatively, either ketone may be converted into its corresponding oxime by using hydroxylamine or hydroxylamine acid salts such as hydroxylamine or hydrochloride whereby an oxime having the structure: ##STR148## is formed. Such ketals and oximes also have useful organoleptic properties.

Process 7:

In the reaction of the 2-acyl-3,3-dimethylnorbornane or the 2-acyl-3,3-dimethyl-5-norbornene with the Grignard reagent having the structure: ##STR149## wherein R₁, R₂ and R₁₀ are separately hydrogen or lower alkyl and X is one of the halogen atoms, chlorine, bromine or iodine, the reaction conditions are essentially the same as those of the corresponding reaction in Process (2) and the recovery steps are essentially the same. R₈ ' of the generic structure: ##STR150## is defined wherein R₈ ' is lower alkyl such as methyl, ethyl, n-proyl, i-propyl, n-butyl, i-butyl, n-pentyl and n-octyl. The resulting alcohol having the structure: ##STR151## can be esterified in accordance with the corresponding reaction detailed in the Process (3) description, supra.

                                      TABLE I                                      __________________________________________________________________________                                                           Tobacco                  Structure of Compound                                                                             Name of Compound                                                                          Perfumery Evaluation                                                                        Flavor Evaluation                                                                         Evaluation               __________________________________________________________________________      ##STR152##        2(2-butenoyl)- 3,3-dimethyl- norbornane                                                   Sweet, woody, fruity, spicey (nutmeg,                                          pepper), herbaceous aroma with pine neodic                                     nuances.     Fruity, pine needle/ green,                                                    winey aroma with piney,                                                        eugenol/ clove, spicey,                                                        fruity, winey flavor.               cis and trans                                                                   ##STR153##        2-(3'-butenoyl)-3,3- dimethylnorbornane                                                   Fruity, herbaceous, piney aroma with                                           armoise character and fir-balsam character-                                    stics.       Fruity-estery, cedarwood,                                                      floral, woody, balsam tree                                                     resin-like aroma with sweet,                                                   fruity, banana-like, estery,                                                   balsam tree resin- like, piney                                                 flavor character.                    ##STR154##         alpha-allyl-3,3- dimetthyl-2-norbor- nanemethanol                                        Sweet, woody, thujone- like arome with                                         armoise, cedar leaf, piney                                                     and camphoraceous nuances.                                                                  A sweet, fruity berry aroma                                                    with woody, incense, warm                                                      tea-like, floral nuances and                                                   as incense and cedarwood                                                       flavor with rosey, berry and                                                   tea nuances.                                                                              A woody, sweet,                                                                fruity, cooling                                                                aroma and taste                                                                before and on                                                                  smoking.                  ##STR155##        alpha-methallyl- 3,3-dimethyl-2- norbornanemethanol                                       Fruity, musty, sweet, woody, minty aroma                                       with fresh cut pine/spruce nuances.                                                         Incense and woody aroma and an                                                 ncense and woody flavor with                                                   astrin- gent and bitter notes.       ##STR156##        alpha-ethyl-3,3- dimethyl-2-norbor- nanemethanol                                          Musty, sweet fruity, woody aroma with                                          artemesia character- istics.                                                                A sweet, woody, minty aroma                                                    with camphoraceous green/                                                      earthy nuances and a woody,                                                    green and minty flavor with                                                    spicey, earthy, red beet-like                                                  and cam- phoraceous nuances as                                                 well as a cool- ing effect.          ##STR157##        endo-2(2'-butenoyl)- 3,3-dimethyl-5- norbornone                                           Woody, piney, natural- like aroma with                                         fruity, spicey, cresylic, bor- neol                                            nuances, as well as a definitive berry top                                     note.        Balsam, blueberry, piney,                                                      green fruity, woody aroma with                                                 alsam natural-like, balsom                                                     resin-like piney, woody and                                                    blueberry flavor characteristic                                                s.                                   ##STR158##        Mixture of 2- acetyl-2-allyl-3,3- dimethylnorbor- nane                         and 3,3-dim- ethyl-2-(4'-penten- oyl)-norbornane                                          Camphoraceous, woody, fruity (orange) aroma                                    ith green, piney undertones.                      ##STR159##        2-(cis-2'-buten-1'- oyl)-3,3-dimethy)- norbornane                                         Intense, piney, fruity, with floral, berry                                     and cologne nuances.                              ##STR160##        3,3-dimethyl-2-(4'- pentenoyl)-norbor- nane                                               A sweet, fruity, fir- balsam, floral aroma                                     with woody and pine- apple                                                                  Sweet, fruity, pine- apple,                                                    green, woody, apple                                                            juice-like, piney aroma char-                                                  acter with berry, piney,                                                       oriental- like and woody                                                       flavor character.                    ##STR161##        3,3-dimethyl-2- pentanoylnorbor- nane                                                     Sweet, fruity, fir- balsam aroma with                                          floral (ylang, jasmin) and berry                                                            A sweet fruity/ berry,                                                         raspberry, woody and plum                                                      aroma with sweet, fruity/berry,                                                 raspberry, val- erian                                                         oil-like, woody and plum                                                       flavor character- istics.            ##STR162##        3,3-dimethyl-alpha- propyl-2-norbornane- methanol                                         Camphoraceous, woody, green aroma with                                         minty nuances.                                                                              A sweet, delicate piney,                                                       fruity, berry- like, valerian                                                  oil- like, woody aroma with                                                    sweet, delicate piney,                                                         evergreen- like, valerian oil-                                                 ike, fruity, berry and                                                         astringent flavor characteristi                                                cs.                                  ##STR163##        2-butyryl-3,3- dimethylnorbornane                                                         A sweet, piney needle- like, fruity,                                           camphor- aceous aroma.                                                                      A sweet, delicate, piney,                                                      fruity, fir balsam needle oil-                                                 ile, blueberry, woody and                                                      straw- berry-like aroma with                                                   sweet, delicate piney,                                                         blueberry, juniper-like,                                                       straw- berry and astringent                                                    nuances.                             ##STR164##        Mixture of 3,3- dimethyl-2(4'- methyl-4'-pentenoyl)-                           norbornane and 3,3- dimethyl-2-acetyl- 2(2'-methyl-2'-                         ropenyl)-norbornane                                                                       A fruity, woody, low- keyed but long                                           lasting aroma.                                                                              A camphoraceous, woody and                                                     minty aroma with a strong                                                      cooling nuance and a strong,                                                   woody and minty                                                                           A woody aroma,                                                                 prior to and on                                                                smoking with sweet,                                                            spicey, floral                                                                 nuances.                  ##STR165##                                                                     ##STR166##        2-acetyl-2-meth- allyl-3,3-dimethyl- norbornane                                           A low-keyed, sweet, camphoraceous, woody                                       (cedarwood) aroma with green, herbaceous                                       and piney nuances.                                ##STR167##        3,3-dimethyl-2-(2- methallyl-4'- methyl-4'-penten-                             oyl)-norbornane                                                                           A low-keyed, sweet, green, woody, herb-                                        aceous aroma with a waxy nuance.                 Mixture of:        Mixture of 3,3-                                                                           A long lasting,                                                                             A fruity, rasp-                                                                           A sweet, fruity-          ##STR168##        dimethyl-2-(4'- methyl-2'-penten- oyl)-norbornane;                             3,3-dimethyl-2-(4'- methyl-3'-pentenoyl)- norbornane;                          and 3,3- dimethyl-2-(4'-methyl- 3-methoxypentenoyl)-                           norbornane excellent, fruity and berry                                                                 berry and sweet aroma with a                                                   green nuance and a fruty,                                                      rasp- berry, green flavor with                                                 a bitter nuance.                                                                          raspberry-like                                                                 aroma prior to                                                                 smoking and a                                                                  sweet, fruity,                                                                 raspberry aroma                                                                with green nuances                                                             on smoking, when                                                               used in both the                                                               tobacco and in the                                                             filter.                  Mixture of:        Mixture of 3,3-dim-                                                                       A fruity, berry-like                                                                        A sweet, red                                                                              A sweet, floral           ##STR169##        ethyl-2-(4'-methyl- 2'-penenoyl)-5- norbornene;                                3,3-dim- ethyl-2-(4'-methyl- 3-pentenoyl)-5- norbornene                        ; and 3,3- dimethyl-2-(4'-methyl- 3-methoxypentenoyl)-                         -norbornene                                                                               aroma.       berry jam-like, fruity aroma                                                   with citrus, ionone-like,                                                      berry-like, pine needle-like                                                   and pungent nuances and a                                                      fruity, red berry-like, berry                                                  jam-like flavor with green,                                                    fresh raspberry and piney                                                      nuances.   and green aroma                                                                prior to smoking,                                                              and a sweet,                                                                   fruity, floral                                                                 aroma on smoking in                                                            the mainstream and                                                             in the side-                                                                   stream.                   ##STR170##        alpha-ethyl-3,3- dimethyl-2-nor- bornanemethanol                                          A minty, sweet fruity, woody aroma with                                        some artemesia character and, in addition,                                     herbaceous and pine needle                                                                  A sweet, woody, minty aroma                                                    with green and earthy nuances                                                  and a woody, green, minty                                                      flavor with spicey, earthy,                                                    cooling and red beet                                                                      A sweet, woody,                                                                piney aroma and a                                                              strong, cooling                                                                effect when used in                                                            the filter, both                                                               prior to, and, on                                                              smoking. Also                                                                  reduces harshness                                                              and gives rise to a                                                            "fresh" effect.           ##STR171##        alpha-allyl-alpha- 3,3-trimethyl-2- norbornanemethanol                                    Low-keyed, sweet, woody (cut pine)                                                          Sweet, earthy, piney,                                                          cedarwood aroma with sweet,                                                    cedarwood, fruity, blueberry-li                                                ke flavor with patch- ouli and                                                 walnut nuances.                      ##STR172##        alpha-allyl-alpha- 3,3-trimethyl-5- norbornane-2-                              methanol   A sweet, minty, fruity, slight melony,                                         woody aroma. A piney, fruity, woody,                                                        patchouli- like, carrot,                                                       walnut aroma with a sweet,                                                     fruity, woody, camphora-                                                       ceous, carrot,  dried apple,                                                   patchouli-like, walnut and                                                     astrin- gent                        __________________________________________________________________________                                                flavor.                        

When the norbornane derivatives of our invention are used as food flavor adjuvants, the nature of the co-ingredients included with each of the said norbornane derivatives in formulating the product composition will also serve to alter, modify, augment or enhance the organoleptic characteristics of the ultimate foodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and "augment" in their various forms mean "supplying or imparting flavor character or note to otherwise bland, relatively tasteless substances or augmenting the existing flavor characteristic where a natural flavor is deficient in some regard or supplementing the existing flavor impression to modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of a flavor or aroma characteristic or note without the modification of the quality thereof. Thus, "enhancement" of a flavor or aroma means that the enhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquid ingestible materials which usually do, but need not, have nutritional value. Thus, foodstuffs include soups, convenience foods, beverages, dairy products, candies, vegetables, cereals, soft drinks, snacks and the like.

As used herein, the term "medicinal product" includes both solids and liquids which are ingestible non-toxic materials which have medicinal value such as cough syrups, cough drops, aspirin and chewable medicinal tablets.

The term "chewing gum" is intended to mean a composition which comprises a substantially water-insoluble, chewable plastic gum base such as chicle, or substitutes therefor, including jelutong, guttakay, rubber or certain comestible natural or synthetic resins or waxes. Incorporated with the gum base in admixture therewith may be plasticizers or softening agents, e.g., glycerine; and a flavoring composition which incorporates one or more of the norbornane derivatives of our invention, and in addition, sweetening agents which may be sugars, including sucrose or dextrose and/or artificial sweeteners such as cyclamates or saccharin. Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoring adjuvants are well known in the art for such use, being extensively described in the relevant literature. It is a requirement that any such material be "ingestibly" acceptable and thus non-toxic and otherwise non-deleterious particularly from an organoleptic standpoint whereby the ultimate flavor and/or aroma of the consumable material used is not caused to have unacceptable aroma and taste nuances. Such materials may in general be characterized as flavoring adjuvants or vehicles comprising broadly stabilizers, thickeners, surface active agents, conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride; antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2- and 3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene (2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like and sequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids, suspending agents, emulsifiers and the like, e.g., agar agar, carrageenan; cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose; natural and synthetic gums such as gum arabic, gum tragacanth; gelatin, proteinaceous materials; lipids; carbohydrates; starches, pectines, and emulsifiers, e.g., mono- and diglycerides of fatty acids, skim milk powder, hexoses, pentoses, disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids such as capric acid, caprylic acid, palmitic acid,myristic acid and the like, mono- and diglycerides of fatty acids, lecithin, defoaming and flavor-dispersing agents such as sorbitan monostearate, potassium stearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents, e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; starch modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, proylene oxide, succinic anhydride and the like, buffers and neutralizing agents, e.g., sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, vinegar and the like; colorants, e.g., carminic acid, cochineal, tumeric and curcuma and the like; firming agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; texturizers, anti-caking agents, e.g., aluminum calcium sulfate and tribasic calcium phosphate; enzymes; yeast foods, e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g., iron salts such as ferric phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfate and the like.

Other flavorants and flavor intensifiers include aldehydes, esters, natural oils, alcohols, sulfides, ketones, lactones, carboxylic acids and hydrocarbons such as heliotropin, terpinenol-4, benzaldehyde, anisaldehyde, phenyl acetaldehyde, benzyl formate, benzyl acetate, cis-3-hexenyl benzoate, methyl hexanoate, hexanal, eucalyptol, eugenol, acetaldehyde, ethyl acetate, ethyl butyrate, turpentine gum oil, limonene, gum camphor, isobornyl acetate, borneol, cinnamic aldehyde, cuminic aldehyde, furfural, methyl cinnamate, cassia oil, vanillin, maltol, parahydroxybenzyl acetone, dimethyl sulfide, alpha-ionone, acetic acid, isobutyl acetate, acetone, butyric acid, formic acid, valeric acid, amyl acetate, amyl butyrate, anethol, benzyl salicylate, diacetyl, dimethyl anthranilate, ethyl methylphenylglycidate, ethyl succinate, ethyl valerate, geraniol, cis-3-hexen-1-ol, 2-hexenyl acetate, 2-hexenyl butyrate, hexyl butyrate, 4-(p-hydroxyphenyl)-2-butanone, beta-ionone, isobutyl cinnamate, jasmine, lemon essential oil, methyl butyrate, methyl caproate, methyl disulfide, methyl p-naphthyl ketone, orris butter, rose absolute, terpenyl acetate, gammaundecalactone, vanilla and alcohol.

The specific flavoring adjuvant selected for use may be either solid or liquid depending upon the desired physical form of the ultimate product, i.e., foodstuff, whether simulated or natural, and should, in any event, (i) be organoleptically compatible with the norbornane derivatives of our invention by not covering or spoiling the organoleptic properties (aroma and/or taste) thereof; (ii) be non-reactive with the norbornane derivatives of our invention and (iii) be capable of providing an environment in which the norbornane derivatives can be dispersed or admixed to provide a homogeneous medium. In addition, selection of one or more flavoring adjuvants, as well as the quantities thereof will depend upon the precise organoleptic character desired in the finished product. Thus, in the case of flavoring compositions, ingredient selection will vary in accordance with the foodstuff, chewing gum, medicinal product or toothpaste to which the flavor and/or aroma are to be imparted, modified, altered or enhanced. In contradistinction, in the preparation of solid products, e.g., simulated foodstuffs, ingredients capable of providing normally solid compositions should be selected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of norbornane derivatives employed in a particular instance can vary over a relatively wide range, depending upon the desired organoleptic effects to be achieved. Thus, correspondingly, greater amounts would be necessary in those instances wherein the ultimate food composition to be flavored is relatively bland to the taste, whereas relatively minor quantities may suffice for purposes of enhancing the composition merely deficient in natural flavor or aroma. The primary requirement is that the amount selected to be effective, i.e., sufficient to alter, modify or enhance the organoleptic characteristics of the parent composition, whether foodstuff per se, chewing gum, per se, medicinal product per se, toothpaste per se, or flavoring composition.

The use of insufficient quantities of norbornane derivatives will, of course, substantially vitiate any possibility of obtaining the desired results while excess quantities prove needlessly costly and, in extreme cases, may disrupt the flavor-aroma balance, thus proving self-defeating. Accordingly, the terminology "effective amount " and "sufficient amount" is to be accorded a significance in the context of the present invention consistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gum compositions, medicinal product compositions and toothpaste compositions, it is found that quantities of norbornane derivatives ranging from a small but effective amount, e.g., 0.5 parts per million up to about 500 parts per million based on total composition are suitable. Concentrations in excess of the maximum quantity stated are not normally recommended, since they fail to prove commensurate enhancement of organoleptic properties. In those instances, wherein the norbornane derivatives are added to the foodstuff as an integral component of a flavoring composition, it is, of course, essential that the total quantity of flavoring composition employed be sufficient to yield and effective norbornane derivative concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the present invention preferably contain the norbornane derivatives in concentrations ranging from about 0.1% up to about 15% by weight based on the total weight of the said flavoring composition.

The composition described herein can be prepared according to conventional techniques well known as typified by cake batters and fruit drinks and can be formulated by merely admixing the involved ingredients within the proportions stated in a suitable blender to obtain the desired consistency, homogeneity of dispersion, etc. Alternatively, flavoring compositions in the form of particulate solids can be conveniently prepared by mixing the norbornane derivatives with, for example, gum arabic, gum tragacanth, carrageenan and the like, and thereafter spray-drying the resultant mixture whereby to obtain the particular solid product. Pre-prepared flavor mixes in powder form, e.g., a fruit-flavored powder mix are obtained by mixing the dried solid components, e.g., starch, sugar and the like and norbornane derivatives in a dry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the norbornane derivatives of our invention, the following adjuvants:

Heliotropin;

Terpinenol-4;

Benzaldehyde;

Anisaldehyde;

Phenyl acetaldehyde;

Benzyl formate;

Benzyl acetate;

Cis-3-hexenyl benzoate;

Methyl hexanoate;

Hexanal;

Eucalyptol;

Eugenol;

Acetaldehyde;

Ethyl acetate;

Ethyl butyrate;

Turpentine gum oil;

Limonene;

Gum camphor;

Isobornyl acetate;

Borneol;

Cinnamic aldehyde;

Cuminic aldehyde;

Furfural;

Methyl cinnamate,

Cassia oil;

Vanillin;

Maltol;

Parahydroxybenzylacetone;

Dimethyl sulfide;

Alpha-ionone;

Acetic acid;

Isobutyl acetate;

Acetone;

Butyric acid;

Formic acid;

Valeric acid;

Amyl acetate;

Amyl butyrate;

Anethol;

Benzyl salicylate;

Diacetyl;

Dimethyl anthranilate;

Ethyl methylphenylglycidate;

Ethyl succinate;

Ethyl valerate;

Geraniol;

Cis-3-hexen-1-ol;

2-Hexenyl acetate;

2-Hexenyl butyrate;

Hexyl butyrate;

4-(p-Hydroxyphenyl)-2-butanone;

Beta-ionone;

Isobutyl cinnamate;

Jasmine;

Lemon essential oil;

Methyl butyrate;

Methyl capronate;

Methyl disulfide;

Methyl p-naphthyl ketone;

Orris butter;

Rose absolute;

Terpenyl acetate;

Gamma-undecalactone,

Vanilla; and

Alcohol.

The following Examples serve to illustrate specific embodiments of our invention.

It will be understood that these Examples are illustrative and the invention is to be restricted thereto only as indicated in the appended claims.

All parts and percentages are given by weight unless otherwise specified.

EXAMPLE I Preparation of 3,3-dimethyl-2-norbornanecarboxaldehyde Reaction: ##STR173## Procedure:

Into a 3 liter flask fitted with a stirrer, addition funnel, reflux condenser and thermometer are placed the following materials:

    ______________________________________                                         Camphene (80%)           500 g                                                 Methylene chloride       500 cc                                                Sodium carbonate         300 g                                                 ______________________________________                                    

The slurry is stirred while 600 cc of peracetic acid (40%) is added over a six hour period. The temperature rises until the mixture is at reflux (44° C. in the beginning, 48° C. at the end of the addition). The course of the reaction is monitored by GLC. The mixture is allowed to stir for 2 hours after the completion of the addition. The salts are then removed by filtration. The methylene chloride is stripped off and 500 cc of benzene is added. The mixture is azeotroped using a water separation trap to remove traces of water. After all water is removed, the mixture (670 g) is ready for use in the next step. A GLC (samples are prepared by dissolving the salts in water, separating the organic layer and washing it several times with water. The GLC conditions are: 10'×1/8" SE-30 column, programmed at 80°-200° at 8° C. per minute) indicated 26% benzene, 9.6% tricyclene and 61.2% camphene oxide, corresponding to a yield of 408 g of camphene oxide, or 92% of theory.

50 Grams of magnesium bromide is added and the mixture is refluxed for four hours. At the end of this time a GLC analysis (10'×1/8" Carbowax 20M column, programmed from 80°-220° C. at 8° C./minute) shows complete conversion of the camphene oxide to 3,3-dimethyl-2-norbornanecarboxaldehye.

EXAMPLE II Preparation of alpha-allyl-3,3-dimethyl-2-norbornanemethanol Reaction: ##STR174## Procedure:

Into a 3 liter reaction flask fitted with a stirrer, reflux condenser, thermometer, dropping funnel and a N₂ bleed, is added 55 g of magnesium turnings (2.26 moles) and 1 liter of anhydrous tetrahydrofuran. The apparatus is blanketed with dry N₂, and 2 moles of allyl chloride (152 g, 162 ml) is placed in the addition funnel; about 10 cc is added at once with stirring. When the reaction begins (exotherm to 30°), the flask and contents are cooled to 0° C. (dry ice/isopropyl alcohol bath) and the remainder of the allyl chloride is added over a 3 hour period while the temperature is kept at 0°-5°. When addition is complete the contents of the flask are stirred for an additional hour while warming to 22° C. at room temperature. The Grignard solution is decanted from the excess magnesium into another reaction flask and 330 g of a solution of 3,3-dimethyl-2-norbornanecarboxaldehyde in benzene prepared as in Example I (62% aldehyde by GLC area normalization) is added over one hour. The reaction is exothermic and the temperature rises until the solution refluxes (65°-70° C.). At the end of the addition, the mixture is heated and refluxed for an additional 1/2 hour. The Grignard complex is hydrolyzed by the addition of about 400 cc of 15% HCl (to a pH of 1). The aqueous layer is separated and extracted with 200 cc of benzene. The combined organic layers are stripped on a rotary evaporator and the residue is distilled through a 1' stone packed column after adding thereto 30 g of Primol®, at 70°-77° C. at 0.2-0.25 mm Hg pressure, yielding 206 grams product. The resulting product is essentially one peak by GLC analysis (conditions: 10'×1/8" SE-30 column, programmed at 80°-220° C. at 8°/min.). This corresponds to a yield of 92% theory based on 3,3-dimethyl-2-norbornanecarboxaldehyde added. This peak consists of a compound having the structure:

    ______________________________________                                          ##STR175##                                                                    NMR Data:                                                                      ______________________________________                                         0.92 ppm                                                                                 singlets, methyl protons                                                                          (3H each)                                         0.98                                                                           1.0-2.4   complex signals                                                      4.85-5.20 multiplet, CHCH.sub.2                                                                             2H                                                5.68-6.08 multiplet, CHCH.sub.2                                                                             1H                                                ______________________________________                                    

mass spectral data: m/e=69, 55, 41, 111, 67, 109

Infrared data: cm⁻¹ 3475 (--OH), 3079 (--CH═CH₂)

The NMR spectrum is set forth in FIG. 1.

The Infrared spectrum is set forth in FIG. 2.

EXAMPLE III Preparation of 2-(3-butenoyl)-3,3-dimethylnorbornane using a sodium dichromate-sulfuric acid-benzene oxidizing system Reaction: ##STR176## Procedure:

Sulfuric acid (60 cc, 110 g) is added slowly to 300 ml water with stirring. When the solution cools to room temperature, 300 cc (263 g) of benzene and 50 g of alpha-allyl-3,3-dimethyl-2-norbornanemethanol is added. The mixture is stirred at room temperature and 20 g of sodium dichromate is added. After one hour a second 20 g portion is added. After an additional one hour of stirring the layers are separated. The benzene layer is washed with saturated NaHCO₃ solution and then with water. The solvent is stripped and the residue is distilled rapidly to yield two distillation fractions. The first distillation fraction has a boiling point range of 65°-97° C. at 1.2 mm and weighs 2.5 g. The second distillation fraction has a boiling point range of 97°-99° C. at 1.0 mm Hg and weighs 39.4 grams, corresponding to a yield of 80% of theory.

The second distillation fraction is primarily a compound having the structure: ##STR177##

This compound is purified by means of column chromatography on a column of silicic acid (deactivated by the addition of 5% water). The compound is eluted with a mixture of 2% diethyl ether in isopentane. Thus, from 1.5 grams of this second distillation fraction was obtained, after solvent stripping, 1.0 grams of an oil which was distilled on a micro distillation apparatus, yielding pure 2-(3-butenoyl)-3,3-dimethylnorbornane (i), having the following spectral characteristics:

    ______________________________________                                          ##STR178##                                                                    NMR data:                                                                      δ, ppm            Interpretation                                         ______________________________________                                         0.95                                                                           1.0                     methyl singlets                                        1.18                    (endo and exo isomers)                                 1.24                                                                           1.0-2.5                 complex signals                                        3.12                                                                                     ##STR179##    doublet of quartets                                    6.1                                                                            6.9      CH.sub.2CHCH.sub.2                                                                            multiplets                                             ______________________________________                                    

Mass Spectral Data: m/e=123, 41, 67, 81, 39, 151

Infrared Data: cm⁻¹ 1720 (normal carbonyl)

The NMR spectrum for this compound is set forth in FIG. 5. The Infrared spectrum is set forth in FIG. 6.

When either crude or purified 2-(3-butenoyl)-3,3-dimethylnorbornane is subjected to GLC analysis, a second material is observed. This material is trapped and identified as cis-2-(3-butenoyl)-3,3-dimethylnorbornane (ii), having the following spectral characteristics:

    ______________________________________                                         (ii) Structure:                                                                 ##STR180##                                                                    NMR data:                                                                      δ, ppm             Interpretation                                        ______________________________________                                         0.85                                                                           0.96                     methyl singlets                                       1.20                     (endo and exo isomers)                                1.24                                                                           1.88                                                                                     ##STR181##     doublet of triplets                                   1.0-2.5                  complex singals                                       6.12 6.76                                                                                ##STR182##     multiplets                                            ______________________________________                                    

Mass Spectral Data: m/e=41, 69, 125, 67, 81, 108, 123

Infrared Datum: cm⁻¹ 1685 (conjugated carbonyl)

The NMR spectrum is set forth in FIG. 3. The Infrared spectrum is set forth in FIG. 4.

EXAMPLES IV-X Oxidation and attempted oxidation of alpha-allyl-3,3-dimethyl-2-norbornanemethanol

Using different oxidizing agents, the following Examples, as set forth in Table I, are performed with the results indicated whereby 2-(3-butenoyl)-3,3-dimethylnorbornane is produced in a number of reactions and is not produced where "no reaction" is indicated:

                  TABLE I                                                          ______________________________________                                         Ex-   Quantity                                                                 ample of Alcohol                                                                               Oxidizing Agent and                                            No.   Reactant  Conditions      Results                                        ______________________________________                                         IV              Jones Reagent at room                                                                          Mixture of                                                     temperature.    many products                                                                  formed.                                        V     50 g      Na.sub.2 Cr.sub.2 O.sub.7 (40 g)/H.sub.2 SO.sub.4                                              Successful oxid-                                               (60 cc)/benzene ations; 50% con-                                               (300 cc); room temp-                                                                           version to ketone.                                             erature for 2 hours.                                           VI     1 g      10 ml dimethyl sul-                                                                            No reaction.                                                   foxide/5 g acetic                                                              anhydride at 60° C.                                     VII   10 g      Copper chromite (1 g)/                                                                         No reaction.                                                   200° C. for 1 hour.                                     VIII   5 g      Pyridinium chloro-                                                                             50% conversion                                                 chromate (8.5 g)                                                                               to ketone.                                                     (prepared according                                                            to Corey, Tetrahedron                                                          Letters, 31, 2647,                                                             1975); methylene                                                               dichloride (50 cc);                                                            room temperature; 1                                                            hour.                                                          IX     5 g      Chromium trioxide                                                                              50% conversion                                                 (2.5 g)/acetic acid                                                                            to ketone.                                                     (5 ml)/water (50 ml);                                                          room temperature; 1                                                            hour.                                                          X     15 g      Jones reagent (25 ml)                                                                          90% conversion                                                 (prepared according                                                                            to ketone.                                                     to Example IV)/acetone                                                         (15 ml),-5° C., 2 hours.                                ______________________________________                                    

EXAMPLE XI Preparation of endo-2-(trans-2-butenoyl)-3,3-dimethyl-5-norbornene Reaction: ##STR183##

Into a three necked flask equipped with a condenser, thermometer, mechanical stirrer and cooling bath (dry-ice-isopropyl alcohol) is charged 666 grams (3.0 moles) of 3 M methylmagnesium chloride in tetrahydrofuran. To this is added a solution of 321 grams (3.0 moles) of methyl aniline in 300 ml of benzene over a 30 minute period, keeping the reaction temperature at 20°-30° C. The reaction is exothermic and methane gas is evolved. When the gas evolution ceases a solution of 510 g (3.0 moles) of endo-2-acetyl-3,3-dimethyl-5-norbornene (prepared by AlCl₃ catalyzed reaction of cyclopentadiene and mesityl oxide, U.S. Pat. No. 3,852,358) in 300 ml of benzene is added over 40 minutes with the temperature kept at 20°-30° C. The mixture is stirred at room temperature for one hour and then cooled to 0° C. At this temperature 132 g (3.0 moles) of acetaldehyde in 300 ml of benzene is added over 30 minutes. After an additional 30 minutes at 0° C., 600 g of 37% HCl diluted with 1200 ml of water is added. After another 15 minutes at 0° C. the layers are separated. The organic layer is washed twice with water and dried over MgSO₄. The solvent is evaporated keeping the liquid temperature below 45° C. The residue is then combined with 600 ml of acetic anhydride and 150 g of sodium acetate, stirred and heated to 100° C. for 2 hours. The mixture is cooled to 80° C. and water is added to destroy excess acetic anhydride. The mixture is cooled, washed with water, saturated NaHCO₃ solution and dried over MgSO₄. The product is distilled without fractionation to give 204 g of an oil, b.p. 70°-130° C. (1.0-1.5 mm). This material contained about 50% starting ketone and a mixture of reaction products. The major reaction product is isolated by redistillation followed by preparative GLC on a 6'×1/4" column packed with 10% Carbowax 20 M. On the basis of its NMR spectrum the product is predominantly the endo isomer (>90%): ##STR184##

The NMR spectrum is set forth in FIG. 7. The Infrared spectrum is set forth in FIG. 8.

EXAMPLE XII Preparation of 2-(2-butenoyl)-3,3-dimethylnorbornane (primarily the "trans" isomer) Reaction: ##STR185##

Into a 2 liter autoclave the following materials are placed:

    ______________________________________                                         Ingredients         Quantity                                                   ______________________________________                                         2-acetyl-3,3-dimethyl-                                                         norbornane          644 g (4 moles)                                            acetaldehyde        132 g (3 moles)                                            boron oxide         105 g (1.5 moles)                                          boron acid          12 g (0.2 moles)                                           ______________________________________                                    

The autoclave is sealed and the contents are heated at 150° C. for a period of 3 hours at autogeneous pressure. At the end of the 3 hour period the contents of the autoclave are cooled to room temperature and filtered. The filter cake is washed with 250 ml cyclohexane and the filtrate is distilled rapidly through a 2" column, after adding thereto 20 g Primol® and 0.1 g Ionox® to give 649 g of oil collected at 77°-129° C. and a pressure of 2.7-4.0 mm Hg. This material is then fractionally distilled on a 12"×1" Goodloe column, after adding thereto Primol® and Ionox®, to give 490 g of oil collected at 73°-78° C. and a pressure of 3.3-4 mm Hg. The resulting material, insofar as its fragrance properties are concerned, has a sweet, woody, fruity, spicey and herbaceous aroma with pine needle nuances. Insofar as flavor characteristics are concerned, this material has a fruity, pine needle/green, winey aroma with a piney, eugenol/clove, spicey, fruity and winey flavor.

NMR, Infrared and Mass Spectral analyses confirm that the resulting structure is:

    ______________________________________                                          ##STR186##                                                                    NMR data:                                                                      δ, ppm            Interpretation                                         ______________________________________                                         0.82                                                                           0.93                    singlets, methyl protons                               1.16                    (endo and exo isomers)                                 1.20                                                                           1.28     CHCH.sub.3     doublet of doublets                                    1.0-2.5                 complex signals                                        6.1 6.7                                                                                  ##STR187##    multiplets 1H each                                     ______________________________________                                    

Mass Spectral Data: m/e=69, 41, 125, 39, 67, 108

Infrared Data: cm⁻¹ 1690 (conjugated carbonyl)

The NMR spectrum is set forth in FIG. 9. The Infrared spectrum is set forth in FIG. 10.

EXAMPLE XIII Preparation of 2-(2-butenoyl)-3,3-dimethylnorbornane Reaction: ##STR188##

Into a 2 liter autoclave the following materials are placed:

    ______________________________________                                         Ingredients         Quantity                                                   ______________________________________                                         2-acetyl-3,3-dimethyl-                                                         norbornane          830 g (5 moles)                                            acetaldehyde         88 g (2 moles)                                            boron oxide          50 g (0.71 moles)                                         ______________________________________                                    

The autoclave is sealed and the contents thereof are heated to 170°-185° C. and maintained at that temperature for two hours during which time the pressure within the autoclave is 50 psig. At the end of the two hour period the reaction mass is cooled to room temperature and decanted, and the resulting liquid, after adding thereto 20 g Primol® and 0.1 g Ionox®, is distilled rapidly through a 2" column, to yield 625 g of crude material collected at 77°-129° C. and a pressure of 2.7-4.0 mm Hg. The resulting material, after adding thereto Primol® and Ionox®, is then fractionally distilled through a 12"×1" Goodloe column at 73°-78° C. and a pressure of 3.3-4 mm Hg. The major peak is trapped on a GLC column yielding a material having the structure: ##STR189## as confirmed by GLC, IR and NMR analyses.

The material has a fruity aroma with piney and musty nuances insofar as its fragrance properties are concerned and a fruity and berry aroma with waxy, berry, sour and bitter flavor characteristics insofar as its taste properties are concerned.

EXAMPLE XIV Blueberry flavor formulation

The following formulation is prepared:

    ______________________________________                                         Ingredients          Parts by Weight                                           ______________________________________                                         Heliotropin          3.0                                                       Terpihenol-4 (10% in 95% aqueous                                                 food grade ethanol)                                                                               0.2                                                       Benzaldehyde         1.5                                                       Anisaldehyde         0.2                                                       Phenyl acetaldehyde  0.4                                                       Benzyl formate       0.5                                                       Benzyl acetate       2.0                                                       Cis-3-hexenyl benzoate (10% in 95%                                               aqueous food grade                                                             ethanol)           0.5                                                       Methyl hexanoate     2.0                                                       Hexanal              1.0                                                       Eucalyptol (1% in 95% aqueous                                                    food grade ethanol)                                                                               0.5                                                       Eugenol              0.2                                                       Acetaldehyde         3.0                                                       Ethyl acetate        21.0                                                      Ethyl butyrate       26.0                                                      Propylene glycol     38.0                                                                           100.0                                                     ______________________________________                                    

The above formulation is split into 2 portions. To the first portion is added, at the rate of 1%, 2-(2-butenoyl)-3,3-dimethylnorbornane. The second portion contains nothing added thereto. Both formulations, with and without the said 2-(2-butenoyl)-3,3-dimethylnorbornane (produced according to Example XII), are combined with water at the rate of 100 ppm. The flavor with the 2-(2-butenoyl)-3,3-dimethylnorbornane, prepared according to Example XII, has a more winey, fruity, piney character and is closely similar to the flavor of wild blueberries. It is therefor preferred to the basic blueberry formulation which does not contain said 2-(2-butenoyl)-3,3-dimethylnorbornane.

EXAMPLE XV Flavor use of alpha-allyl-3,3-dimethyl-2-norbornanemethanol

The following basic cinnamon formulation is prepared:

    ______________________________________                                         Ingredients      Parts by Weight                                               ______________________________________                                         Cinnamic aldehyde                                                                               70                                                            Eugenol          15                                                            Cuminic aldehyde 1                                                             Furfural         0.5                                                           Methyl cinnamate 5.0                                                           Cassia oil       8.5                                                           ______________________________________                                    

This formulation is split into two parts. To the first part is added, at the rate of 5%, alpha-allyl-3,3-dimethyl-2-norbornanemethanol prepared according to Example II. To the second part no additive is added. The alpha-allyl-3,3-dimethyl-2-norbornanemethanol adds a more cinnamon bark-like character in aroma and taste and a more woody/sweet aroma. It is therefor preferred to the formulation without such additive. The formulations are compared in water at the rate of 10 ppm.

EXAMPLE XVI Preparation of alpha-ethyl-3,3-dimethyl-2-norbornanemethanol Reaction: ##STR190##

Into a 1 liter reaction flask equipped with a stirrer, thermometer, condenser, nitrogen inlet tube and dropping funnel is placed 129 cc of a 2.9 molar solution of ethyl magnesium chloride in tetrahydrofuran. Over a 20 minute period 19.0 g of 3,3-dimethyl-2-norbornanecarboxaldehyde is added with stirring. The reaction is exothermic. The reaction mass is then refluxed for a period of 3 hours. At the end of the 3 hour period the reaction mass is cooled to room temperature, and 100 cc of saturated ammonium chloride solution is added thereto. The organic layer is then extracted with 500 cc diethyl ether, and the extract is concentrated and distilled through a micro Vigreux column after adding thereto 3 g of Primol®.

Mass spectral, NMR and infrared analysis of the distilled product, b.p. 85° C. at 1.5 mm Hg, indicates that it has the structure:

    ______________________________________                                          ##STR191##                                                                    NMR data:                                                                      δ, ppm        Interpretation                                             ______________________________________                                         0.96                                                                           singlets            gem dimethyl                                               1.02                                                                           1.04 triplet        CH.sub.2CH.sub.3                                           1.0-2.4 multiplet                                                                                   ##STR192##                                                3.5 multiplet                                                                                       ##STR193##                                                ______________________________________                                    

mass Spectral Data: m/e=67, 41, 121, 81, 59, 182 (parent peak)

From a food flavor standpoint the resulting material has a sweet, woody, minty aroma with camphoraceous, green and earthy nuances and a woody, green, minty flavor with spicey, earthy, cooling, red beet-like and camphoraceous nuances at 5 ppm. From a perfumery standpoint the resulting material has a musty, sweet, fruity, woody aroma with an artemesia character.

This material has a significant utility in tobacco filter flavors where it lends a cooling effect with sweet, woody and piney notes both prior to and during smoking, when 10 micro liters of a 10% solution is added to the filter.

The NMR spectrum is set forth in FIG. 11.

The Infrared spectrum is set forth in FIG. 12.

EXAMPLE XVII Use of alpha-ethyl-3,3-dimethyl-2-norbornanemethanol

The following basic raspberry formulation is prepared:

    ______________________________________                                         Ingredients             Parts by Weight                                        ______________________________________                                         Vanillin                2                                                      Maltol                  4                                                      Parahydroxy benzyl actone                                                                              5                                                      Dimethyl sulfide        1                                                      Alpha-ionone (10% in propylene glycol)                                                                 2                                                      Ethyl butyrate          6                                                      Ethyl acetate           16                                                     Isobutyl acetate        14                                                     Acetic acid             10                                                     Acetaldehyde            10                                                     Propylene glycol        930                                                                            1000                                                   ______________________________________                                    

The above formulation is split into two parts. To the first part, at the rate of 0.3% is added alpha-ethyl-3,3-dimethyl-2-norbornanemethanol produced according to Example XVI. No additive is added to the second part. The two formulations are compared in water at the rate of 50 ppm. The flavor containing the alpha-ethyl-3,3-dimethyl-2-norbornanemethanol has a more ripe raspberry taste and a woody, raspberry kernel character. Therefore, the raspberry formulation containing the norbornane derivative as an additive has a more natural like and more characteristic raspberry flavor and is therefor preferred.

EXAMPLE XVIII Preparation of alpha-methallyl-3,3-dimethyl-2-norbornanemethanol Reaction: ##STR194##

Into a 3 liter reaction flask equipped with a stirrer, condenser, nitrogen inlet tube, thermometer and dropping funnel are placed 24 g of magnesium with just enough tetrahydrofuran to cover it. Two milliliters (approximately 20 cc) of methallyl chloride is then added to start the reaction. When the reaction is well under way, 500 cc of tetrahydrofuran is added, and 90.5 g of methallyl chloride is added dropwise over a period of 2 hours while maintaining a steady reflux. After the final addition, refluxing is continued for a period of one hour. Fifty grams of norbornane aldehyde, produced according to Example I, dissolved in 100 cc of toluene is then added over a period of 20 minutes, and the reaction mass is again refluxed for a period of 3 hours. The reaction mass is then cooled to room temperature, and 100 cc of saturated aqueous ammonium chloride solution is then added thereto. The reaction mass is then extracted with diethyl ether and the diethyl ether extract is concentrated. The concentrate is then distilled on an 8"×11/2" porcelain saddle packed column after adding thereto 5 g of Primol®.

The distilled product, b.p. 100° C. at 2.0 mm Hg, is subjected to NMR, IR, Mass Spectral and UV analyses confirming that the structure is:

    ______________________________________                                          ##STR195##                                                                    NMR data:                                                                      δ, ppm         Interpretation                                            ______________________________________                                         0.94                                                                           singlets             gem dimethyl                                              1.0                                                                            1.77 singlet                                                                                         ##STR196##                                               1.0-2.4 multiplet                                                                                    ##STR197##                                               4.72 multiplet                                                                                       ##STR198##                                               ______________________________________                                    

mass Spectral Data: m/e=69, 41, 55, 43, 69, 208 (parent peak).

The resulting material has a musty, sweet, woody, minty aroma with an intense, fresh cut pine/spruce nuance.

The NMR spectrum is set forth in FIG. 13.

The Infrared spectrum is set forth in FIG. 14.

EXAMPLE XIX Preparation of 2-(4'-methyl-2'-pentenoyl)-3,3-dimethylnorbornane Reaction: ##STR199##

Into a 3 liter reaction flask equipped with a stirrer, thermometer, reflux condenser, addition funnel and nitrogen inlet tube the following materials are added:

    ______________________________________                                         Ingredient         Amount                                                      ______________________________________                                         methanol           500 g                                                       potassium hydroxide                                                                                56 g                                                       toluene             50 g                                                       2-acetyl-3,3-dimethyl-                                                         norbornane         500 g                                                       ______________________________________                                    

The reaction mass is heated to reflux for a period of 1 hour at which time 240 g (3.3 moles) of isobutyraldehyde is added over a period of 20 minutes. When the addition is complete, the reaction mass is stirred for an additional 4 hours at a temperature of 72° C. At the end of the four hour period, 50 g of concentrated HCl is added to the reaction mass. The reaction mass is then admixed with 1 liter of water and 500 ml of toluene. The aqueous phase is then extracted with one 250 ml portion of toluene, and the toluene is combined with the organic layer which is washed as follows:

two 250 ml portions of water;

one 500 ml portion of 5% sodium bicarbonate solution; and

one 250 ml portion of saturated sodium chloride solution.

The crude material is then stripped of solvent using a Buchi evaporator, and the stripped crude (after adding thereto 25 g Primol® and 1 g Ionox®) is rapidly distilled using a 2" column. The distilled material is then fractionated on a 12" Goodloe packed column after adding thereto 30 g Primol® and 1 g Ionox®.

GLC, NMR, Infrared and Mass Spectral analyses yield the information that the resulting material is a mixture of three compounds having the structures: ##STR200##

The GLC profile is set forth in FIG. 15.

The NMR spectrum for the mixture of compounds having the structures: ##STR201## is set forth in FIG. 16. The Infrared spectrum is set forth in FIG. 17.

The NMR spectrum for the mixture of ketones having the structures: ##STR202## is set forth in FIG. 18. The Infrared spectrum for this mixture of ketones is set forth in FIG. 19.

The NMR spectrum for the compound having the structure: ##STR203## is set forth in FIG. 20. The Infrared spectrum for this keto-ether compound is set forth in FIG. 21.

    ______________________________________                                         Structural Assignments                                                         I. Mixture of A and B                                                          Infrared Data:                                                                   1618.sup.-1, 1705, 1698                                                      NMR Data (CDCl.sub.3):                                                         ppm                   Interpretation                                           ______________________________________                                         6.70       doublet of doublets (J ≈ 16 Hz, 7Hz)                                                   ##STR204##                                          6.00       doublet of doublets (J ≈ 6 Hz, 1 Hz)                                                   ##STR205##                                          5.28       broad triplet (J ≈ 6 Hz)                                                               ##STR206##                                          3.03       broad doublet (J ≈ 6 Hz)                                                               ##STR207##                                          1.74, 1.63 broad singlets                                                                                 ##STR208##                                          1.23, 0.87, 0.83                                                                          singlets                                                                                       ##STR209##                                          1.07       doublet (J ≈ 6 Hz)                                                                     ##STR210##                                          ______________________________________                                    

comparison of the integrals for the signals at 6.70 and 6.00 ppm with the signal at 5.28 ppm shows that the ratio of A/B is approximately 1/1.

    ______________________________________                                         II. Compound C                                                                 NMR Data:                                                                      ppm               Interpretation                                               ______________________________________                                         3.50    1H multiplet                                                                                  ##STR211##                                              3.34, 3.31                                                                             3H two singlets                                                                               ##STR212##                                                                    (asymmetric                                                                    center)                                                  1.24 0.85                                                                              3H singlet 3H singlet                                                                         ##STR213##                                              0.89    6H doublet (J ≈ 5 Hz)                                                                 ##STR214##                                              ______________________________________                                    

infrared Datum: 1705 cm⁻¹

The overall mixture of the three compounds in Fraction 12, from a food flavor standpoint, has a fruity, raspberry, sweet aroma with a green nuance and a fruity, raspberry, green flavor with a bitter nuance at 5 ppm. The mixture of ketones A and B, from a perfumery standpoint, has a long lasting fruity, berry-like aroma with chocolate, spicey, winey, sweet, balsamic, fruity, pineapple, raspberry, cinammon, ionone-like, musty, floral, woody, salicyl and amyris nuances. When used with tobacco it has a sweet, fruity, raspberry-like, green aroma prior to smoking, and adds a sweet, fruity, green taste to the tobacco smoke flavor when used at 200-500 ppm levels in tobacco.

EXAMPLE XX Preparation of 2-(4'-methyl-2'-pentenoyl)-3,3-dimethyl-5-norbornene Reaction: ##STR215##

Into a 3 liter reaction flask equipped with a stirrer, thermometer, reflux condenser and addition funnel are placed a solution of 56 g of potassium hydroxide in 500 g of methanol. While maintaining the methanol/KOH solution at 2°-4° C., a solution of 500 g (3 moles) of 2-acetyl-3,3-dimethyl-5-norbornene, 240 g (3.3 moles) of isobutyraldehyde, and 50 g of toluene is added from the addition funnel over a period of 35 minutes.

The reaction mass is then stirred for a period of one hour at 2°-4° C. and for a period of 12 hours at 71° C. to 73° C., while refluxing. The reaction mass is then cooled and transferred to a separatory funnel and mixed with 1 liter of water and 500 ml toluene. The aqueous layer is separated and extracted with one 250 ml portion of toluene. The organic layer is combined with the toluene extract and is washed with:

one 500 ml portion of water;

one 500 ml portion of 5% sodium bicarbonate solution; and

one 500 ml portion of saturated aqueous sodium chloride solution.

The crude organic material is then stripped at solvent and distilled rapidly after adding thereto 25 g Primol® and 1 gram Ionol®.

The distilled material is then fractionally distilled on a 12" Goodloe column.

GLC, IR, NMR and Mass Spectral analyses yield the information that the resulting material is a mixture of 3 compounds having the structures: ##STR216##

The GLC profile for this mixture is set forth in FIG. 22.

The product, from a food flavor standpoint, has a sweet, red berry jam-like, fruity aroma with citrus, ionone-like, berry, pine-needle and pungent nuances and a fruity, red berry jam flavor with green, fresh raspberry and piney nuances.

From a perfumery standpoint this material has a fruity, berry-like aroma. In tobacco, prior to smoking, this material has a sweet, floral-like, green aroma. On smoking, sweet, fruity and slightly floral nuances are created.

The three materials produced are separated in a GLC column (conditions: 5'×1/4" 5% SE-30 column operated at 200° C. isothermal).

The NMR spectrum for the mixture of compounds having the structures:

    ______________________________________                                          ##STR217##                                                                     ##STR218##                                                                     ##STR219##                                                                    Spectral Data for Total Mixture                                                Infrared Data:                                                                   1620 .sup.cm-1, 1705, 1685, 1660                                             NMR Data:                                                                      ppm              Interpretation                                                ______________________________________                                         6.74    doublet of doublets (J ≈ 16 Hz, 7 Hz)                                                ##STR220##                                               5.95-6.50                                                                              multiplet                                                                                    ##STR221##                                                                     ##STR222##                                               5.34    broad triplet                                                                                ##STR223##                                               1.78 1.66                                                                               broad singlets                                                                              ##STR224##                                               1.13, 1.04, 0.81, 0.79                                                                 singlets                                                                                     ##STR225##                                               1.03    doublet (J ≈ 6 Hz)                                                                   ##STR226##                                               3.80     singlets                                                                                    ##STR227##                                               3.40                 (asymmetric                                                                    center)                                                   ______________________________________                                    

EXAMPLE XXI Preparation of 2-(1-hydroxybutyl)-3,3-dimethylnorbornane and 2-butyryl-3,3-dimethylnorbornane Reaction: ##STR228## PART A

Into a 200 cc flask equipped with a stirrer, thermometer and reflux condenser is placed 15 g of dimethylnorbornanecarboxaldehyde, produced according to the process of Example I, and 50 cc diethyl ether. Over a 15 minute period 50 cc of a solution of n-propyl magnesium chloride (2.2 molar in diethyl ether) is added to the aldehyde. The reaction mass is then refluxed for a period of one-half hour whereupon a GLC analysis indicated complete reaction of the norbornanecarboxaldehyde. The resulting reaction mass is then hydrolyzed with saturated aqueous ammonium chloride solution, and water is then added to dissolve the salts. The water phase is extracted with 50 cc of diethyl ether, and the ether extract is combined with the organic phase and stripped. The product is distilled on a micro Vigreux column yielding 13.3 grams in 5 fractions, b.p. 79°-82° C. at 1 mm Hg.

    ______________________________________                                         NMR Data:                                                                      δ, ppm    Interpretation                                                 ______________________________________                                         0.88                                                                           1.02                    singlets, gem dimethyl                                 1.01                    protons (2 sets; 2 isomers                             1.25                    exo and endo)                                          1.06    triplet         CH.sub.3CH.sub.2                                       2.34-1.32               methylene and methine                                                          protons                                                3.56    multiplet                                                                                       ##STR229##                                            1.13    singlet         OH                                                     ______________________________________                                    

infrared Data: 950, 1005, 1055, 1100, 1355, 1375, 1455, 2860, 2920, 2950, 3360 cm⁻¹

Mass Spectral Data: m/e=41, 135, 55, 67, 43, 27; parent peak=196

The NMR spectrum is set forth in FIG. 25. The Infrared spectrum is set forth in FIG. 26.

PART B

A 2.5 g portion of the distillate produced in Part A is dissolved in 10 cc of acetone and the resulting solution is cooled to 0°-5° C. while a "Jones Reagent" prepared according to Example IV is added dropwise (2 ml total required). GLC analysis indicates one product is formed. 25 cc of water is added to the reaction mass, and the aqueous phase is extracted with diethyl ether. The diethyl ether extract and the organic phase are combined and washed with saturated sodium chloride solution. The washed organic solution is stripped and distilled on a micro Vigreux column yielding 1.3 grams of product, distilling at 90° C. and 1.0 mm Hg pressure.

NMR, IR and Mass Spectral analyses confirm that the compound is 2-butyryl-3,3-dimethylnorbornane.

    ______________________________________                                         NMR Data:                                                                      δ, ppm     Interpretation                                                ______________________________________                                         0.84                                                                           0.90                                                                           0.95             CH.sub.2 CH.sub.3 ; CH.sub.3 ; endo and                       1.14             exo isomers                                                   1.31                                                                           1.0-1.06         multiplets                                                    2.3triplet                                                                                       ##STR230##                                                   ______________________________________                                    

infrared Datum: 1700 cm⁻¹ (C═O)

Mass Spectral Data: m/e=123, 43, 41, 127, 27, 67; parent peak=194

The NMR spectrum is set forth in FIG. 27. The Infrared spectrum is set forth in FIG. 28.

EXAMPLE XXII Preparation of 2-butyroyl-3,3-dimethylnorbornane Reaction: ##STR231##

Into a 250 cc Parr shaker the following materials are placed:

    ______________________________________                                         Ingredient          Quantity                                                   ______________________________________                                         2-(trans-2-butenoyl)-3,3-                                                      dimethylnorbornane                                                             prepared according to                                                          the process of Example                                                         XII                 90 g                                                       5% palladium-on-carbon                                                         catalyst             1 g                                                       ______________________________________                                    

The Parr shaker is sealed and then pressurized up to 50 psig with hydrogen and periodically repressurized over a period of 7 hours to maintain a pressure of 50 psig. During this period of time the temperature of the reaction mass remains at 25° C. At the end of the 7 hour period the Parr shaker is opened and the contents removed and filtered. To the filtrate, 5.0 g of Primol® and 0.1 g of Ionol® is added. The resulting mixture is then distilled on a four foot Vigreux column to give 47 g of oil, b.p. 93°-95° C. at 3.0 mm Hg.

NMR, IR and Mass Spectral analyses yield the information that the product has the structure:

    ______________________________________                                          ##STR232##                                                                    NMR Data:                                                                      δ, ppm    Assignments                                                    ______________________________________                                         0.85                                                                           0.96            singlets, 2 sets,                                              1.14            (2 isomers)                                                    1.22                                                                           0.89 (t)        CH.sub.3CH.sub.2                                               2.08-1.46       methylene and methine                                                          protons                                                        2.30            diffuse triplet                                                                protons alpha carbonyl                                         ______________________________________                                    

Infrared Data: 1100, 1115, 1290, 1360, 1400, 1455, 1700, 2870, 2940 cm⁻¹

Mass Spectral Data: m/e=123, 41, 43, 127, 27, 151; parent peak=194

The NMR spectrum is set forth in FIG. 29. The Infrared spectrum is set forth in FIG. 30.

EXAMPLE XXIII Preparation of 2-(4'-pentenoyl)-3,3-dimethylnorbornane Reaction: ##STR233##

Into a 500 ml reaction flask equipped with a stirrer, thermometer, reflux condenser, addition funnel and nitrogen inlet tube is placed a suspension of 48 g of 55% sodium hydride and 250 ml toluene. Under a nitrogen blanket, 166 g (1 mole) of 2-acetyl-3,3-dimethylnorbornane is added over a period of 5 minutes. The resulting mixture is heated to reflux for a period of 70 minutes and then is cooled to 45° C. Allyl chloride (76 g, 1 mole) and 4 g of tricapryl methyl ammonium chloride (Aliquat 336®, produced by General Mills Chemical Inc.) is added thereto over a period of 15 minutes. The reaction mass is then stirred at 60° C. for a period of 12 hours.

The resulting suspension is allowed to settle, and the reaction mass is filtered through glass wool. The filtrate is washed with water, and the solvent is removed on a rotary evaporator to yield a white milky oil. GLC analysis indicates three peaks. The GLC profile (conditions: 8'×1/4" SE-30 column, programmed at 200° C. isothermal; 40 ml/minute) is set forth in FIG. 31. NMR, IR and Mass Spectral analyses confirm that the 3 compounds produced have the following structures: ##STR234##

The compund having the structure: ##STR235## has the following mass spectral data: m/e=123, 81, 67, 55, 151, 108, 83; parent peak=206

The NMR data for this compound is as follows:

    ______________________________________                                         δ, ppm      Interpretation                                               ______________________________________                                         0.88Δsinglet                                                                               gem dimethyl group                                           1.22Δsinglet                                                             4.92                                                                           5.05              --CH=CH.sub.2                                                5.12                                                                           5.65-5.95         --CH.sub.2 --CH=CH.sub.2                                     ______________________________________                                    

The NMR spectrum is set forth in FIG. 32.

The compound having the structure: ##STR236## has the following NMR analysis:

    ______________________________________                                         δ, ppm      Interpretation                                               ______________________________________                                         1.04 singlet                                                                                     gem dimethyl group                                           1.02 singlet                                                                   2.05 singlet                                                                                      ##STR237##                                                  2.40 J = 7Hz doublet                                                                             CH.sub.2CHCH.sub.2                                           4.92 multiplet                                                                                   CHCH.sub.2                                                   5.96 multiplet                                                                 5.3-5.8 multiplet CH.sub.2CHCH.sub.2                                           ______________________________________                                    

the NMR spectrum for this compound is set forth in FIG. 33.

The compound having the structure: ##STR238## has the following NMR data:

    ______________________________________                                         δ, ppm      Interpretation                                               ______________________________________                                         0.88 singlet                                                                                     gem dimethyl group                                           1.20 singlet                                                                   4.92-5.14 multiplet                                                                              --CH=CH.sub.2                                                5.5-5.9 multiplet --CH=CH.sub.2                                                ______________________________________                                    

The NMR spectrum is set forth in FIG. 34. The Infrared spectrum is set forth in FIG. 35. The Infrared data is as follows:

1700 cm⁻¹ (C═O); 1635 cm⁻¹ (C═C)

From a perfumery standpoint, the product has a camphoraceous, woody, fruity (orange) aroma with green and piney undertones.

A process similar to that carried out above is carried out with the exception that instead of sodium hydride, a molar equivalent of sodium hydroxide is used. The results are that the same three compounds are produced in the following percentages and in the following ratios:

    ______________________________________                                         Structure             Percent   Ratio                                          ______________________________________                                          ##STR239##           24        1.3                                             ##STR240##           19        1                                               ##STR241##           57        3                                              ______________________________________                                    

example xxiv production of 2-(4'-pentenoyl)-3,3-dimethylnorbornane Part A Reaction: ##STR242## Part B Reaction: ##STR243## Part A:

Into a 3 liter reaction flask equipped with a nitrogen inlet tube, thermometer, reflux condenser and stirrer the following materials are placed:

    ______________________________________                                         sodium hydride (55%)   88 g                                                    diethyl carbonate      236 g                                                   benzene                1 liter                                                 ______________________________________                                    

Under a nitrogen blanket the resulting mixture is heated to reflux.

Over a period of 30 minutes, 2-acetyl-3,3-dimethylnorbornane is added to the reaction mass. At the end of the addition, the reaction mass is refluxed for an additional 40 minutes. Two hundred milliliters of acetic acid followed by 1 liter of water are added to the reaction mass. The organic phase is separated, and the resulting crude material is distilled rapidly using a 2" splash column to give 205 g of oil, b.p. 80°-160° C. at 1 mm Hg.

After 5 g of Primol® is added to the distilled material, it is fractionally distilled on a 12"×1" Goodloe distillation column to give 119 g of product, b.p. 109°-127° C. at 1.2 mm Hg.

The distilled material is confirmed by NMR analysis to have the structure:

    ______________________________________                                          ##STR244##                                                                    NMR Data:                                                                      δ, ppm      Interpretation                                               ______________________________________                                         0.92 singlet                                                                                     gem dimethyl group                                           1.22 singlet                                                                   1.24 (J = 7Hz) triplet                                                                           CH.sub.2 CH.sub.3                                            3.35 singlet                                                                                      ##STR245##                                                  4.18 (J = 7Hz) quartet                                                                           OCH.sub.2 CH.sub.3                                           ______________________________________                                    

the NMR spectrum is set forth in FIG. 36. The Infrared spectrum is set forth in FIG. 37.

Infrared Data: 1650 --C═C (m); 1700 C═O (strong) ##STR246##

Mass Spectral Data: m/e=108, 123, 109, 107, 29, 41; parent peak=238

Part B:

One hundred grams of toluene are admixed with 24 g (0.55 moles) of sodium hydride and heated to 60° C. in a 500 cc reaction flask equipped with a stirrer, thermometer and reflux condenser. Over a period of 80 minutes the carboethoxy compound produced in Part A is added to the toluene/sodium hydride mixture. At the end of the addition of the ketocarboxylic acid ester compound, a mixture of 38.5 g of allyl chloride and 7 g of tricapryl methyl ammonium chloride (Aliquat 336®, produced by General Mills Chemical Inc.) is added over a 20 minute period while maintaining the reaction mass at 80° C.

Fifty milliliters of 50% sodium hydroxide solution and 50 ml of water is then added to the reaction mass, and the resulting mixture is refluxed for a period of 2 hours. Water (100 ml) is then added to dissolve the resulting precipitate. Then 110 ml of 20% hydrochloric acid is added with the evolution of carbon dioxide gas.

The resulting product is then distilled rapidly at 100° C. and 2 mm Hg pressure, and the distilled product (after adding thereto 10 g of Primol® and 1 g of Ionox®) is fractionated to give an oil, b.p. 90° C./1.0 mm Hg.

The product is confirmed by NMR and Infrared analyses to have the structure: ##STR247##

The NMR spectrum is set forth in FIG. 38.

    ______________________________________                                         NMR Data:                                                                      δ, ppm      Interpretation                                               ______________________________________                                         0.88 singlet                                                                                     gem dimethyl group                                           1.22 singlet                                                                   4.92-5.12 multiplet                                                                              --CH=CH.sub.2                                                5.65-5.95 multiplet                                                                              --CH.sub.2 --CH=CH.sub.2                                     ______________________________________                                    

The Infrared spectrum is set forth in FIG. 39.

Infrared Data: 1630 (C═C), 1700 cm⁻¹ (C═O)

EXAMPLE XXV Preparation of 2-pentanoyl-3,3-dimethylnorbornane Reaction: ##STR248##

10 g of 2-(4'-pentenoyl)-3,3-dimethylnorbornane produced according to Part B of Example XXV and 50 ml of isopropyl alcohol is placed in a Parr shaker along with 0.5 g of palladium catalyst. The Parr shaker is sealed and pressurized with hydrogen up to 30 psig and over a 2 hour period is repressurized with hydrogen as needed to maintain the pressure at 30 psig. During this period of time the temperature of the reaction mass remains at 25° C. At the end of the 2 hour period the mass is filtered. The solvent is then evaporated and the product is isolated using preparative GLC.

NRM, Mass Spectral and Infrared analyses confirm that the resulting product has the structure: ##STR249## This material has a sweet, berry, mandarin orange aroma with piney nuances.

    ______________________________________                                         NMR Data:                                                                      δ, ppm        Interpretation                                             ______________________________________                                         1.86 singlet                                                                                       gem dimethyl group                                         2.24 singlet                                                                   0.88 (J ≈ 6Hz) triplet                                                                     CH.sub.2 CH.sub.3                                          2.30 (J ≈ 7Hz) triplet                                                                      ##STR250##                                                2.30 singlet                                                                                        ##STR251##                                                ______________________________________                                    

mass Spectral Data: m/e=123, 41, 67, 81, 57, 108; parent peak=208

Infrared Datum: 1700 cm⁻¹ (>C═O)

The NMR spectrum is set forth in FIG. 40. The Infrared spectrum is set forth in FIG. 41.

EXAMPLE XXVI Preparation of alpha-methallyl-alpha,3,3-trimethyl-5-norbornene-2-methanol Reaction: ##STR252##

Into a 1 liter reaction flask equipped with a reflux condenser, thermometer, stirrer, dropping funnel and nitrogen inlet tube are placed 12 g (0.5 moles) of magnesium turnings and 250 cc anhydrous diethyl ether. Over a 2 hour period, 45.3 g (0.5 moles) of methallyl chloride is added. The Grignard solution is stirred for 1/2 hour and 28 g of 2-acetyl-3,3-dimethyl-5-norbornene is added over a 20 minute period. The mixture is stirred at reflux for 1/2 hour and then is hydrolyzed by the addition of saturated ammonium chloride solution. The organic solution is washed with water and dried over magnesium sulfate. The mixture is then filtered and the solvent evaporated to yield 40 g of an oil, which is then fractionated on a micro Vigreux column after adding thereto 5 g Primol® and a trace quantity of Ionox®.

Mass Spectral, Infrared and NMR analyses confirm that the resulting compound has the structure:

    ______________________________________                                          ##STR253##                                                                    NMR Data:                                                                      δ,ppm     Interpretation                                                 ______________________________________                                         1.40-0.97       methyl protons                                                 1.86            CCH.sub.3                                                      2.36-1.48       methylene and methine                                                          protons                                                        4.84-4.78                                                                                       ##STR254##                                                    6.24-1.12       olefinic protons of                                                            norbornene ring                                                ______________________________________                                    

Infrared Data: 700, 880, 1080, 1320, 1360, 1450, 2950, 3500 cm⁻¹.

The NMR spectrum is set forth in FIG. 42. The Infrared spectrum is set forth in FIG. 43.

EXAMPLE XXVII Preparation of alpha-allyl-alpha,3,3-trimethyl-2-norbornane-methanol Reaction:

    ______________________________________                                          ##STR255##                                                                     ##STR256##                                                                     ##STR257##                                                                    Ingredient          Quantity                                                   ______________________________________                                         2-acetyl-3,3-dimethyl-                                                         norbornane          28.5  g (0.17 moles)                                       magnesium           12.0  g (0.5  moles)                                       allyl chloride      38.25 g (0.5  moles)                                       anhydrous ether     200 cc                                                     ______________________________________                                    

The magnesium turnings are placed into a 1 liter, 3 neck reaction flask, followed by 200 cc of anhydrous ether. Approximately 6 cc of allyl chloride is added to initiate formation of the Grignard reagent. When the reaction is initiated, the remaining allyl chloride is added dropwise over a 2 hour period, with moderate reflux. After the addition, reflux is continued for 1 hour; at which time 28.5 g 2-acetyl-3,3-dimethylnorbornane is introduced over a 20 minute period. The reaction is very exothermic during this addition. At the end of the addition, refluxing is continued for 1 hour. The work up is carried out by hydrolyzing with NH₄ Cl solution, filtering and separating the layers. The organic layer is washed with two 200 cc portions of water, dried over MgSO₄, filtered and concentrated to give 34 grams of oil which is distilled to give 26 g of product, b.p. 90°-105° C. at 1-2 mm Hg.

    ______________________________________                                         NMR Data:                                                                      δ, ppm       Assignment                                                  ______________________________________                                         1.06                                                                           1.10                                                                           1.20               methyl protons                                              1.24                                                                           1.26                                                                           1.30                                                                           2.18-1.56          methylene protons                                           2.32                                                                           5.16-5.00                                                                                          ##STR258##                                                 6.08-5.64          HCCH.sub.2                                                  ______________________________________                                    

infrared Data: 910, 1085, 1160, 1200, 1250, 1300, 1330, 1360, 1385, 1460, 2860, 2940, 3070, 3480 cm⁻¹.

The NMR spectrum is set forth in FIG. 44. The Infrared spectrum is set forth in FIG. 45.

EXAMPLE XXVIII Preparation of alpha-allyl-alpha,3,3-trimethyl-5-norbornene-2-methanol Reaction: ##STR259##

Into a 1 liter 3 necked reaction flask equipped with a stirrer, thermometer, condenser, drying tube and nitrogen inlet are placed the following materials:

    ______________________________________                                         Ingredients         Quantity                                                   ______________________________________                                         2-acetyl-3,3-dimethyl-5-                                                       norbornene          29.2 g (0.17 moles)                                        magnesium           12.0 g (0.5 moles)                                         allyl chloride      38.25 g (0.5 moles)                                        anhydrous ether     200 cc                                                     ______________________________________                                    

This reaction is carried out under the same conditions as the reaction of Example XXVII. The work up is carried out by hydrolyzing with NH₄ Cl solution, filtering and separating the layers. The organic layer is washed with two 200 cc portions of water, dried over MgSO₄, filtered and concentrated to give 37.0 grams of crude product. The crude product is distilled on a micro Vigreux column after adding thereto 5 grams of Primol® and a trace quantity of Ionox® to give 23 g of oil, b.p. 90°-98° C. at 1.0-1.6 mm Hg.

    ______________________________________                                         NMR Data:                                                                      δ, ppm     Interpretation                                                ______________________________________                                         1.38-0.94        methyl protons                                                2.40-1.50        methylene and methine                                                          protons                                                       5.20-5.00        HC═CH.sub.2                                               6.02-5.66        HC═CH.sub.2                                               6.28-6.04        norbornene olefinic                                                            protons                                                       ______________________________________                                    

Infrared Data: 710, 910, 995, 1085, 1140, 1250, 1325, 1360, 1460, 1635, 2960, 3060, 3470 cm⁻¹.

The NMR spectrum is set forth in FIG. 46. The Infrared spectrum is set forth in FIG. 47.

EXAMPLE XXIX Preparation of alpha-methallyl-alpha,3,3-trimethyl-2-norbornanemethanol Reaction: ##STR260##

Into a 1 liter 3 necked flask equipped with a stirrer, thermometer, condenser, drying tube and nitrogen inlet are placed the following materials:

    ______________________________________                                         Ingredients         Quantity                                                   ______________________________________                                         2-acetyl-3,3-dimethyl-                                                         norbornane          28.5 g (0.17 moles)                                        magnesium           12.0 g (0.5 moles)                                         methallyl chloride  45.27 g (0.5 moles)                                        ______________________________________                                    

This reaction is carried out under the same conditions as the reaction of Example XXVII. The work up is carried out by hydrolyzing with NH₄ Cl solution, filtering and separating the layers. After stripping off the solvent, 34 grams of product remains. The resulting product is then distilled on a micro Vigreux column after adding thereto 5 grams Primol® and a trace quantity of Ionox®.

    ______________________________________                                         NMR Data:                                                                      δ, ppm     Interpretation                                                ______________________________________                                         1.27-1.06        methyl protons                                                1.86             CCH.sub.3                                                     2.12-1.32                                                                                        ##STR261##                                                   4.74-4.94                                                                                        ##STR262##                                                   ______________________________________                                    

infrared Data: 880, 1080, 1105, 1360, 1380, 1455, 1630, 2860, 2940, 3500 cm⁻¹.

The NMR spectrum is set forth in FIG. 48. The Infrared spectrum is set forth in FIG. 49.

EXAMPLE XXX Preparation of 3,3-dimethyl-2-(4-methyl-4-pentenoyl)-norbornane Reaction: ##STR263##

A suspension of 146 g of sodium hydride (55% mineral oil dispersion) in 1500 g of toluene is heated to 100° C. and a solution of 500 g of 2-acetyl-3,3-dimethylnorbornane in 250 g of toluene is added over a period of 1 hour. The mixture is stirred at 100°-103° C. until no further hydrogen gas is evolved (total gas evolved=66 liters at 1 atmosphere).

A solution of 280 g of methallyl chloride in 250 g of toluene is then added over a period of 1 hour at 100°-105° C. The mixture is stirred at 100°-110° C. for an additional 14 hours and then cooled to room temperature. The mixture is washed several times with water and the solvent is recovered at atmospheric pressure. The solvent free material is distilled rapidly through a short column under reduced pressure, and the distillate is carefully fractionated using a 12"×1" Goodloe packed column to give (i) 214 g of an oil, b.p. 100°-111° C./0.9 mm Hg, which is shown by GLC profile illustrated in FIG. 50 to be a mixture of (A) 3,3-dimethyl-2-(4'-methyl-4'-pentenoyl)-norbornane and (B) 2-acetyl-2-methallyl-3,3-dimethylnorbornane in the approximate ratio of 3:1 and (ii) 78 g of an oil, b.p. 122° C./0.8 mm Hg, which was essentially pure (C) 3,3-dimethyl-2-(2'-methallyl-4'-methyl-4'-pentenoyl)-norbornane.

The NMR data for compound A are set forth below:

    ______________________________________                                         δ, ppm                                                                            Interpretation  Structure                                             ______________________________________                                         4.70     multiplet                                                                                       ##STR264##                                           1.74     broadened singlet                                                                               ##STR265##                                           1.24 0.86                                                                               singlet                                                                                         ##STR266##                                           ______________________________________                                    

the Infrared datum for Compound A is set forth below: 1701 cm⁻¹

The NMR spectrum for this compound is set forth in FIG. 51. The Infrared spectrum for this compound is set forth in FIG. 52.

The NMR data for Compound B are set forth below:

    ______________________________________                                         δ,ppm                                                                              Interpretation Structure                                             ______________________________________                                         4.82 4.67 broad singlet                                                                                  ##STR267##                                           2.09      singlet                                                                                        ##STR268##                                           1.69      broad singlet                                                                                  ##STR269##                                           1.10 1.03 singlet                                                                                        ##STR270##                                           ______________________________________                                    

the Infrared datum for Compound B is set forth below: 1690 cm⁻¹

The NMR spectrum for this compound is set forth in FIG. 53. The Infrared spectrum for this compound is set forth in FIG. 54.

The NMR analysis for Compound C are set forth below:

    ______________________________________                                         δ,ppm                                                                              Interpretation Structure                                             ______________________________________                                         4.77      multiplet                                                                                      ##STR271##                                           1.76 1.63 2 broad singlets                                                                               ##STR272##                                           1.22 0.87 2 singlets                                                                                     ##STR273##                                           ______________________________________                                    

the Infrared datum for Compound C is set forth below: 1695 cm⁻¹

The NMR spectrum for this compound is set forth in FIG. 55. The Infrared spectrum for this compound is set forth in FIG. 56.

The mixture of compounds having the structures: ##STR274## from a flavor use standpoint, at the level of 10 ppm, has a camphoraceous, woody, minty aroma with a strong cooling nuance making it useful in dentrifices and mouthwashes. In tobacco, at the level of 200 ppm, it gives cooling and floral notes on smoking. From a perfumery use standpoint, this material has a fruity, woody note which is surprisingly long lasting.

The compound having the structure: ##STR275## has a low-keyed, sweet, camphoraceous, cedarwoody aroma with green herbal and piney notes, from a perfumery use standpoint.

The compound having the structure: ##STR276## from a perfumery use standpoint, has a low-keyed, sweet, green woody, herbal aroma.

EXAMPLE XXXI Sodium borohydride reduction of 2-(2-butenoyl)-3,3-dimethylnorbornane Reaction: ##STR277##

Into a 500 cc three necked reaction flask equipped with a stirrer, condenser and thermometer is placed 82 g (43 moles) of a material containing more than 90% 2-(trans-2-butenoyl)-3,3-dimethylnorbornane (produced according to Example XXI) and 250 g of anhydrous methanol. Over a period of 1 hour, 7 g of sodium borohydride is added to the reaction mass, while the reaction mass remains at 25°-26° C.

The reaction mass is then stirred for a period of 3 hours at 25°-28° C., whereupon another 7 grams of sodium borohydride is added. The reaction mass is then stirred for another 3 hours until no further change in the GLC profile is observed. The resulting mixture is then transferred to a 1 liter flask, and the methanol is stripped off leaving a slurry. To the slurry is added 500 ml water, and the resulting mixture is extracted with 150 ml of cyclohexane. The cyclohexane extract is stripped and distilled rapidly at 100°-115° C. and a vacuum of 2.4-2.6 mm Hg. After adding to the resulting material 5 g Primol® and 0.1 g of Ionol®, the rushed over material is fractionally distilled on a 8 plate Vigreux column at 113°-120° C. vapor temperature and 2.7-4.4 mm Hg pressure (reflux ratio 20:1). Ten fractions are produced of which fractions 2-8 are used for flavor and perfumery work.

The resulting material is primarily a mixture of three compounds having the structures: ##STR278## as confirmed by NMR, IR and Mass Spectral analyses.

The resulting mixture is evaluated at 10% in food grade ethanol, from a perfumery standpoint, and has sweet piney, bornyl acetate-like, berry and somewhat woody notes.

From a flavor standpoint, it has a spicey, valerian oil-like, calamus-like, pine needle-like, herbaceous and fruity aroma character with a valerian oil-like, calamus, pine needle, herbaceous and fruity flavor character at 1 ppm.

The resulting mixture has uses in spice flavors, cordial flavors, pine needle flavors and root beer flavors.

The GC-MS profile for the compound having the structure: ##STR279## is set forth in FIG. 57.

The GC-MS profile for the compound having the structure: ##STR280## is set forth in FIG. 58.

The GC-MS profile for the compound having the structure: ##STR281## is set forth in FIG. 59.

The GC-MS profile for the mixture of remaining compounds in the reaction product is set forth in FIG. 60. 

What is claimed is:
 1. A process for augmenting or enhancing the flavor or aroma of a foodstuff comprising adding to said foodstuff from about 0.5 ppm up to about 500 ppm based on the weight of the foodstuff of a norbornane derivative or mixture of norbornane derivatives having the structure or structures:

    ______________________________________                                         Mixture of         Mixture of                                                  Cis & Trans                                                                    Isomers of:                                                                     ##STR282##                                                                                        ##STR283##                                                                    and                                                                             ##STR284##                                                  ##STR285##                                                                                    ##STR286##                                                     Mixture of                                                                     Cis & Trans                                                                    Isomers of:                                                                     ##STR287##                                                                    Mixture of         Mixture of                                                   ##STR288##                                                                                        ##STR289##                                                 ______________________________________                                    


2. the process of claim 1 wherein the norbornane derivative has the structure: ##STR290##
 3. The process of claim 1 wherein the norbornane derivative has the structure: ##STR291##
 4. The process of claim 1 wherein the norbornane derivative is a mixture of cis and trans isomers having the structure: ##STR292##
 5. The process of claim 1 wherein the norbornane derivative has the structure: ##STR293##
 6. The process of claim 1 wherein the norbornane derivative is a mixture of compounds having the structures: ##STR294##
 7. The process of claim 1 wherein the norbornane derivative is a mixture of compounds having the structures: ##STR295##
 8. The process of claim 1 wherein the norbornane derivative is a mixture of compounds having the structure: ##STR296##
 9. A composition useful in augmenting or enhancing the flavor or aroma of a foodstuff comprising (i) from about 0.1% up to about 10% by weight of said foodstuff flavor composition of at least one norbornane derivative or mixture of norbornane derivative having the structures:

    __________________________________________________________________________     Mixture                                                                        Cis & Trans                                                                    Isomers of:                               Mixture of                            ##STR297##                                                                                                               ##STR298##                           ##STR299##                                                                                          ##STR300##                                               Mixture of                                                                     Cis & Trans                                                                    Isomers of:                                                                     ##STR301##                                                                    Mixture of                      Mixture of                                      ##STR302##                                                                                                     ##STR303##                                    __________________________________________________________________________

the remainder of said composition being (ii) at least one adjuvant non-reactive and organoleptically compatible with said norbornane derivative selected from the group consisting of heliotropin, terpinenol-4, benzaldehyde, anisaldehyde, phenyl acetaldehyde, benzyl formate, benzyl acetate, cis-3-hexenyl benzoate, methyl hexanoate, hexanal, eucalyptol, eugenol, acetaldehyde, ethyl acetate, ethyl butyrate, turpentine gum oil, limonene, gum camphor, isobornyl acetate, borneol, cinnamic aldehyde, cuminic aldehyde, furfural, methyl cinnamate, cassia oil, vanillin, maltol, parahydroxy benzyl acetone, dimethyl sulfide, alpha-ionone, acetic acid, isobutyl acetate, acetone, butyric acid, formic acid, valeric acid, amyl acetate, amyl butyrate, anethol, benzyl salicyclate, diacetly, dimethyl anthranilate, ethyl methylphenylglycidate, ethyl succinate, ethyl valerate, geraniol, cis-3-hexen-1-ol, 2-hexenyl acetate, 2-hexenyl butyrate, hexyl butyrate, 4-(p-hydroxyphenyl)-2-butanone, beta-ionone, isobutyl cinnamate, jasmine, lemon essential oil, methyl butyrate, methyl caproate, methyl disulfide, methyl p-naphthyl ketone, orris butter, rose absolute, terpenyl acetate, gamma-undecalactone, vanilla and alcohol and (iii) a vehicle or carrier non-reactive and organoleptically compatible with said adjuvant and said norbornane derivative.
 10. The composition of claim 9 wherein the norbornane derivative has the structure: ##STR304## which structure represents a mixture of cis and trans isomers.
 11. The composition of claim 9 wherein the norbornane derivative has the structure: ##STR305##
 12. The composition of claim 9 wherein the norbornane derivative is a mixture of cis and trans isomers having the structure: ##STR306##
 13. The composition of claim 9 wherein the norbornane derivative has the structure: ##STR307##
 14. The composition of claim 9 wherein the norbornane derivative is a mixture of compounds having the structure: ##STR308##
 15. The composition of claim 9 wherein the norbornane derivative is a mixture of compounds having the structures: ##STR309##
 16. The composition of claim 9 wherein the norbornane derivative is a mixture of compounds having the structures: ##STR310## 